WO2008006136A1 - Improvements in ink formulations comprising gallium naphthalocyanines - Google Patents

Improvements in ink formulations comprising gallium naphthalocyanines Download PDF

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Publication number
WO2008006136A1
WO2008006136A1 PCT/AU2007/000549 AU2007000549W WO2008006136A1 WO 2008006136 A1 WO2008006136 A1 WO 2008006136A1 AU 2007000549 W AU2007000549 W AU 2007000549W WO 2008006136 A1 WO2008006136 A1 WO 2008006136A1
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WO
WIPO (PCT)
Prior art keywords
ink
netpage
formulation
pen
page
Prior art date
Application number
PCT/AU2007/000549
Other languages
French (fr)
Inventor
Sutharsiny Indusegaram
Graciel Gonzaga
Simone Charlotte Vonwiller
Scott Matthew Starling
Lauchlan Everett Hall
Damon Donald Ridley
Kia Silverbrook
Original Assignee
Silverbrook Research Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Silverbrook Research Pty Ltd filed Critical Silverbrook Research Pty Ltd
Priority to KR1020097002439A priority Critical patent/KR101055477B1/en
Priority to AU2007272278A priority patent/AU2007272278B2/en
Priority to CA002656033A priority patent/CA2656033A1/en
Priority to JP2009518675A priority patent/JP2009542865A/en
Priority to EP07718796A priority patent/EP2044088A4/en
Priority to CN200780025932XA priority patent/CN101490062B/en
Publication of WO2008006136A1 publication Critical patent/WO2008006136A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/04—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
    • G06K19/06046—Constructional details

Definitions

  • the present application relates to infrared (IR) dyes, in particular near-IR dyes, which are synthetically accessible in high yield and which are ⁇ spersibJc in an aqueous ink base. It has been developed primarily for providing Bt inks compatible with CMYK inks, and for optimizing IR-absorption
  • IR absorbing dyes have numerous applications, such as optical recording systems, thermal writing displays, laser fitters, infrared photography, medical applications and printing. Typically, it is desirable for the dyes used in these applications to have strong absorption in the near-IR at the emission wavelengths of semiconductor lasers (e.g. between about 700 and 2000 nra, preferably between about 700 and 1000 nm).
  • semiconductor lasers e.g. between about 700 and 2000 nra, preferably between about 700 and 1000 nm.
  • gallium aluminium arsenide (GaAlAs) and indium phosphide (InP) diode lasers are widely used as light sources.
  • IR dyes are in inks, such as printing inks.
  • the storage and retrieval of digital information in printed form is particularly important.
  • a familiar example of this technology is the use of primed, scannable bar codes. Bar codes are typically printed onto tags or labels associated with a particular product and contain information about the product, such a ⁇ its identity, price etc. Bar codes are usually printed in lines of visible black ink, and detected using visible light from a scanner.
  • the scanner typically comprises an LED or laser (e.g. a HeNe User, which emits light at 633 nm) light source and a photocell for detecting reflected light. Black dyes suitable for use in barcode inks are described w, for example, WO03/074613.
  • Netpage systems are the subject of a number of patents and patent applications some of which are listed in the cross-reference section above and , all of which are incorporated herein by reference.
  • the netpage system relies on the production of, and human interaction with, nerpages.
  • Active buttons and hyperlinks oo each page may be clicked with the pen to request information from the network or to signal preferences to a network server.
  • text written by band on a netpage may be automatically recognized and converted to computer text in the netpage system, allowing forms to be filled in.
  • signatures recorded on a nelpage may be automatically verified, allowing e-commerce transactions to be securely authorized.
  • Netpages are the foundation on which a netpage network is built They may provide a paper-based user interface to published information and interactive service.
  • a netpage consists of a printed page (or other surface region) invisibly tagged with references to an online description of the page.
  • the online page description is maintained persistently by a oetpage page server.
  • the page description describes the visible layout and content of the page, including text, graphics and images. It also describes the input elements on the page, including buttons, hyperlinks, and input fields.
  • a oetpage allows markings made with a netpage pen on its surface to be simultaneously captured and processed by the netpage system. Multiple netpages can share the same page description. However, to allow input through otherwise identical pages to be distinguished, each o ⁇ tpage is assigned a unique page identifier. This page ID has sufficient precision to distinguish between a very large number of n ⁇ tpages.
  • Each reference to the page description is encoded in a printed tag.
  • the tag identifies the unique page on which it appears, and thereby indirectly identifies the page description.
  • the tag also identifies its own position on the page.
  • Tags are printed in infrared-absorptive ink on any substrate which is infrared-reflective, such as ordinary paper. Near-infrared wavelengths are invisible to the human eye but are easily sensed by a solid- state image sensor with an appropriate fitter.
  • a tag is sensed by an area image sensor in the netpage pen, and the tag data is transmitted to die netpage system via the nearest netpage printer.
  • the pen is wireless and communicates with the netpage printer via a short-range radio link- Tags are sufficiently small and densely arranged (hat the pen can reliably image at least one tag even on a single click on the page. It is important that the pen recognize the page ID and position on every interaction with the page, since the interaction is stateless. Tags are error-correctably encoded to make them partially tolerant to surface damage.
  • the netpage page server maintains a unique page instance for each printed netpage, allowing it to maintain a distinct set of réelle-s ⁇ ppued values for input fields in the page description for each printed netpage.
  • HyperlabelTM is a trade mark of Silverbrook Research Pty Ltd, Australia.
  • HyperlabelTM systems use an invisible (e.g. infrared) tagging scheme to uniquely identity a product item.
  • This has the significant advantage that it allows the entire surface of a product to be tagged, or a significant portion thereot without impinging on tho graphic design of the product's packaging or labeling. If the entire surface of a product is tagged ("omnitagged"), then the orientation of the product does not affect its ability to be scanned i.e. a significant part of the line-of-sight disadvantage of visible barcodes is eliminated. Furthermore, if the tags are compact and massively replicated (“omiutags”), then label damage no longer prevents scanning.
  • hyperlabelling consists of covering a large portion of the surface of a product with optically- readable invisible tags.
  • tags utilize reflection or absorption in the infrared spectrum, they are referred to as infrared identification (IRID) tags.
  • IRID infrared identification
  • Each HyperlabelTM tag uniquely identifies the product on which it appears.
  • the tag may directly encode the product code of the item, or it may encode a surrogate ID which in turn identifies the product code via a database lookup.
  • Each tag also optionally identifies its own position on the surface of the product item, to provide the downstream consumer benefits of netpage interactivity.
  • HypcrlabelsTM are applied during product manufacture and/or packaging using digital printers, preferably inkjet printers. These may be add-on infrared primers, which print the tags after the text and graphics have been printed by other means, or integrated colour and infrared printers which print the tags, text and graphics simultaneously.
  • Hyperlabels can be detected using similar technology to barcodes, except using a light source having an appropriate near-IR frequency.
  • the light source may be a laser (e.g. a GaAlAs laser, which emits light at 830 run) or it may bo an LED.
  • compatibility of the IR dye wim traditional inkjet inks (i) compatibility of the IR dye with aaiieous solvents used ⁇ inkjet inks; (lii) iflter ⁇ e absorption in the near infra-red region (e g. 700 to 1000 nm); (iv) zero or low intensity visible absorption;
  • IR dyes and ink compositions fulfilling at least some and preferably all of the above criteria.
  • Such inks are desirable to complement n ⁇ tpage and Hyperlabel TM systems.
  • Some [R dyes are commercially available from various sources, such as Epolin Products, Avecia
  • US 5,282,894 describes a solvent-based printing ink comprising a metal-free phthalocyanine, a coraplexed phtbalocyanine, a met ⁇ l-frec rupbtt ⁇ locyanine, a complexed napbtbalocy ⁇ nine, a nickel dithiolene, an aminium compound, a raeihiiie compound or on azulenesqtiaric acid.
  • CMYK inks have a pH in the range of 8-9, so a strongly acidic IR ink would potentially cause precipitation of ink components if the IR and CMYK inks are mixed on a pnnthead face during purging.
  • M is Ga(A 1 );
  • a 1 is an axial ligand selected from -OH, halogen, -OR 1 , -OC(O)R 4 or -O(CH 2 CH 2 O)CR" wherein e i ⁇ an integer from 2 to IO and R' is H, C,. 5 alkyl or C(O)C,. ⁇ ⁇ lkyl.;
  • R 1 and R may be the same or different and are selected from hydrogen or C M2 alkoxy;
  • R 3 is selected from C 11 alkyl.
  • R 4 i ⁇ selected from C
  • R" R y and R* may be the same or different and are selected from C 1 . , 2 alkyL C 3 -I 2 aryl, C5.12 arylalkyl, C,.,j alkoxy, C $ .,j aryloxy or Cj-u arylalkoxy, and each B is independently selected from a base, wherein BH" has a pK, of between 4 and 9
  • an aqueous formulation comprising an JR-absorbing napbtbalocyaoine dye of formula (Tl):
  • M is Ga(A 1 );
  • A' is an axial Ugand selected from -OH, halogen, -OR 1 , -OC(O)R 4 or -O(CH 2 CH 2 O)JR* wherein e is an integer from 2 to 10 and R c is H, C,. ⁇ alkyl or C(O)C 14 alkyl;
  • R 1 and R 2 may be the same or different and are ⁇ elected from hydrogen or C
  • R* i ⁇ selected from C
  • R 1 , K y and R 1 may be the same or different and are selected from C
  • an inkjet ink comprising a dye or a formulation as described above.
  • an inkjet printer comprising a printhead in fluid communication with at least one ink reservoir, wherein said at least one ink reservoir comprises an inkjet ink as described above.
  • an ink cartridge for an inkjet printer wherein said ink cartridge comprises an inkjet ink as described above.
  • ⁇ ⁇ ub ⁇ trate having a dye as described above disposed thereon.
  • ih ⁇ r ⁇ is provided a method of enabling entry of data into a computer syetem via a primed form, the form containing human-readable information and machine-readable coded data, the coded data being indicative of an identity of the form and of a plurality of locations on the form, the method including the steps of: receiving, in the computer system and from a sensing device, indicating data regarding the identity of the form and a position of the sensing device relative to the form, the sensing device, when placed in an operative position relative to the form, generating the indicating data using at least some of the coded data; identifying, in Ae computer system and from the indicating data, at least one field of the form; and interpreting, in the computer system, at least some of the indicating data as it relates to the at least one field, wherein said coded data comprises an IR-absorbing dye as
  • a method of interacting with a product item the product item having a printed surface containing human-readable Information and machine-readable coded data, the coded data being indicative of an identity of the product item
  • the method including the steps of: (a) receiving, in the computer system and from a sensing device, indicating data regarding the identity of the product item, the sensing device, when placed in an operative position relative to the product item, generating the indicating data using at least some of the coded data; and
  • Figure 1 is a schematic of a the relationship betweeo a sample printed netpage and its online page description
  • Figure 2 is a schematic view of a interaction between a netpage pen, a Web terminal, a netpage printer, a netpage relay, a netpage page server, and a netpage application ⁇ erver, and a Web server,
  • Figure 3 illustrates a collection of netpage servers, Web terminals, printers and relays interconnected via a network
  • Figure 4 is a schematic view of a high-level structure of a printed netpage and its online page description
  • Figure 5a is a plan view showing the inKrrUsaving and rotation of the symbols of four codewords of the tag
  • Figure Sb is a plan view showing a roacrodoi layout for the tag shown in Figure 5a;
  • Figure 5c is a plan view showing an arrangement of nine of the tags shown Ln Figures Sa and Sb, in which targets are shared between adjacent tags;
  • Figure Sd is a plan view showing a relationship becween a set of the tags shown in Figure 5a and a field of view of a netpage sensing device in the form of a netpage pen;
  • Figure 6 is a perspective view of a netpage pen and its associated tag-sensing field-of-view cone
  • Figure 7 is a perspective exploded view of the netpage pen shown in Figure 6;
  • Figure 8 is ⁇ schematic block diagram of a pen controller for the netpage pen shown in Figure ⁇ 6 and 7;
  • Figure 9 is a perspective view of a wall-mounted netpage printer.
  • Figure 10 is a section through the length of the netpage printer of Figure 9;
  • Figure H is a detailed view of the ink cartridge, ink, air and glue paths, and print engine ⁇ of the netpage printer of Figures 9 and 10;
  • Figure 12 is an exploded view of an ink cartridge
  • Figure 13 is a schematic view of the structure of an item ID
  • Figure 14 is a schematic view of the structure of an omnitag;
  • Figure 15 is a schematic view of a pen class diagram;
  • Figure 16 is a schematic view of the interaction between a product item, a fixed product 9oann ⁇ r, a hand-held product scanner, a scanner relay, a product server, and a product application server;
  • Figure 17 is a perspective view of a bi-lithic printhead
  • Figure 18 an exploded perspective view of the bi-lithic princhead of Figure 17;
  • Figure 19 is a sectional view through one eod of the bi-lithic printbiad of Figure 17;
  • Figure 20 is a longitudinal sectional view through the b ⁇ -litbic printhead of Figure 17;
  • Figures 21 (a) to 2l(d) show a side elevation, plan view, opposite side elevation and reverse plan view, respectively, of the bi-lithic printhead of Figure 17;
  • Figures 22 (a) to 22(c) show this basic operational principles of a ttusrroal bend actuator;
  • Figure 23 shows a three dimensional view of a single ink jet nozzle arrangement constructed in accordance with Figure 22;
  • Figure 24 shows an array of the nozzle arrangements shown in Figure 23;
  • Figure 25 is a schematic cro ⁇ -sectional view through an ink chamber of a unit cell of a bubble forming heater element actuator.
  • Figure 26 shows a reflectance spectrum of hydroxy ealuwn napbtbalocyBninetet ⁇ ulfonic acid 4;
  • Figure 27 shows a 1 H NMR spectrum of hydroxygallium naphthalocyaninetetrasulfonic acid 4 in 4rDMSO (0.1% w/v);
  • Figure 28 shows a reflectance spectrum of tetrai ⁇ dazouum bydroxygallium oaphthatocyaninetetrasulfonale 7;
  • Figure 29 shows a reflectance spectrum of tetrakis ⁇ BUamnionium) hydroxygallium naphthalocyaninetetrasulfonate 9;
  • Figure 30 shows a reflectance spectrum of tetrakis(DBUaaunonium) hydroxygaJlium napbthalocyaninetetrasulfonate 9 wiihp-toluenesulfonic acid (3 equivalents);
  • Figure 31 shows a reflectance spectrum of tetraimidazolium hydroxygallium naphthalocvantnetetrasulfonate 7 with two equivalents of acetic acid.
  • the term "IR-absorbing dye” means a dye substance, which absorbs infrared radiation and which is therefore suitable for detection by so infrared sensor.
  • the IR-absorbing dye absorbs in the near infrared region, and preferably has a X 0n* in the range of 700 to 1000 ran, more preferably 750 to 900 nm, more preferably 780 to 850 nm.
  • Dyes having a ⁇ in chis range are particularly suitable for detection by semiconductor lasers, such as a gallium aluminium arsenide diode User.
  • dyes represented by formula (I) may be to equilibrium w i th other tautoraers in which me ⁇ -nitrogenfs) of the naphthalocyanine ring system are protonated.
  • the dye represented by formula (T) may only be ⁇ minor species in ttus equilibrium.
  • dye ⁇ according to the present invention are generally represented by formula Q).
  • Other tautomere in equilibrium therewith are, of course, included within the scope of the present invention.
  • Dyes according to the present invention have the advantageous features of: optimal absorption in the near-IR region; suitability for formulation into aqueous inkjet inks; pH compatible with known CMYK inka without sacrificing optimal near-IR absorption; and facile preparation. Moreover, their high extinction coefficients in the near-IR region means that the dyes appear "invisible" at a concentration suitable for detection by a near-IR detector (e.g. a netpage pen). Accordingly, the dyes of the present invention are especially suitable for use in ncrpage and HyperlabelTM applications. None of the dyes known in the prior art has this unique combination of properties.
  • Tbo present invention was initially conceived by observing the reaction of a gallium naphthalocyanine tetiasulfooic acid salt with four equivalents of amine to given an ammonium salt. It was found, surprisingly, that the reflectance 9pectra of ammonium (alts are independent of the structure of the amine, but very much affected by the pK, of the ammonium salt. At low pK « the Q-band (X ⁇ J baa a large monomeric component and is red-shifted to 800-810 ran. However, when strongly basic amines are used, die Q-band exhibits a significant dimer or aggregate component and the monomer component is blue shifted to ⁇ 800 nm.
  • suitable IR ink formulations may be prepared by dissolving a naphtbalocyaninetetrasulfonic acid in an ink vehicle and adjusting the pH of the resulting formulation. It has been round that formulation ⁇ having a pH within the range of 3.5 to 7, or optionally 4 to 6.5, are desirable for achieving a red-shifted Q-band while maintaining CMYK compatibility.
  • the pH may be adjusted using any suitable base (e.g. the conjugate bases of the weak acids described below) or using a buffer solution.
  • the species BIT in the present invention is a week acid having a pKj in the range of 4 to 9, or optionally 4.5 to 8.
  • the dyes of formula (I) may be readily formed by the addition of a base to the corresponding tetrasulfonic acid.
  • the base B may be neutral (e.g. pyridine), in which case BH T will be overall positively charged (e.g. CJUjNH T ).
  • the base may be anionic (e.g. acetate anion) in which case BIT will be overall neutral ⁇ e.g. AcOH).
  • the overall neutrality of the naphthalocyanin ⁇ salt is maintained by a suitable number of metal counterions (e.g. Li", Na * etc).
  • the pK, of some acids are referred to by their corresponding conjugate base.
  • the pK, of pyridine refers to the pK a of the corresponding pyridinium ion.
  • each B is independently selected from the group consisting of a nitrogen base and an oxyanioo. Accordingly, each B may bo a nitrogen base. Alternatively, each B may be an oxyaruon base. Alternatively, there may be a mixture of nitrogen and oxyaoion bases in one dye salt.
  • the four BIT molecules may consist of two molecules of acetic acid and two pyndiniura ions, or alternatively one molecule of acetic and three imidazolium ions. The skilled person will be readily able to conceive of a variecy of mixed dye salts wi ⁇ un the ambit of the present invention.
  • nitrogen base 1 it is meant a base containing at least one nitrogen atom, which can be protonated.
  • the nitrogen base is a C 5 . l2 heteroaryl base, such as imidazole or pyridine. Imidazole is a particularly preferred base in the present invention.
  • ⁇ oxyanion it is meant a base containing at least one oxyanion, which can be protonated.
  • the oxyanion base U a carboxyUt ⁇ base.
  • a carboxylate base is an organic molecule comprising at le ⁇ st one carboxylare (CO 2 * ) moiety.
  • the carboxylate base is of formula R 1 C(O)O", wherein R s is selected from C
  • Examples of carboxylate bases include acetate, benzoate etc.
  • R 1 and R J may be used for modifying or "tuning" the wavelength of X n ⁇ of the dye. Electron-donating substituents (e.g. alkoxy) at the ortho positions can produce a red-sbi ⁇ in the dye.
  • R 1 and R 2 are both Q.g alkoxy groups, preferably butoxy. Butoxy substituents advantageously shift the X n ⁇ towards longer wavelengths in the near infrared, which are preferable for detection by com ⁇ jerciaJly available lasers.
  • R 1 and R J are both hydrogen, which provides an expeditious synthesis of the requisite napnthalocyanioes.
  • the central metal atom M has been found, surprisingly, to have a very significant impact on the tight stability of the compounds of the pw&ent invention.
  • the nature of the organic n ⁇ phth&locysniac chromophore was primarily responsible for the rate at which such compounds degrade-
  • certain meul ⁇ aphthalocyanin ⁇ - show unusually high light stability compared to other metals.
  • gallium and copper napbthalocyanines have been shown to exhibit very good light stability, making these compounds highly suitable for ⁇ e ⁇ age and HyperlabelTM applications in which the IR dye may be exposed to office lighting or sunlight for a year or more.
  • Gallium compounds are particularly preferred since these have a more red-shifted A 1n ⁇ compared to copper.
  • a more red-shifted X 0 ⁇ 1 is preferred, because colored cyan dyes are les ⁇ likely to interfere with the BR dye's response to the netpage pen.
  • a 1 is a hydroxyl group (-OH).
  • a 1 may be selected or modified to impart specific properties onto the dye molecule.
  • a 1 may be selected to add axial si ⁇ nc bulk to the dye molecule, thereby reducing co facial interactions between adjacent dye molecules.
  • the axial ligand when present, adopts a conformation (or is configured) such that it effectively "protects” or blocks a ⁇ -f ⁇ ce of the dye molecule.
  • An axial ligand which can form an "umbrella" over the n-sysiem and reduce cofocial interactions between adjacent dye molecules is particularly suitable for use in the present invention.
  • IR-absorbing dye compounds of the prior an absorb, at least to some extent, in the visible region of the spectrum. Indeed, the vast majority of IR- absorbing dye compounds known in the prior ⁇ are black or green or brown hues of black in the solid state. This visible absorption is clearly undesirable in "invisible" IR inks, especially IR inks for use in oetpage or HyperlabelTM systems.
  • IR-absorbing compounds comprise a ⁇ -system which forms a substantially planar moiety in at least part of the molecule.
  • ⁇ - ⁇ stacking There is a natural tendency for planar n-systems in adjacent molecules to stack on top of each other via cofacial ⁇ -interactions, known as ⁇ - ⁇ stacking.
  • IR-absorbing compounds have a natural tendency to group together via cofacial ⁇ -interactions, producing relatively weakly bound dim ⁇ rs, (rimers etc.
  • ⁇ - ⁇ stacking of IR-absorbing compounds contributes significantly to the production of visible absorption bands in their Ot spectra, which would not otherwise be present in the corresponding monomeric compounds.
  • This visible absorption i ⁇ understood to be due ID broadening of IR absorption bands when ⁇ - systems stack on top of each other and ⁇ -orbitaU interact, producing small changes in their respective energy levels. Broadening of ER absorption bands Ls undesirable in two respects: firstly, it reduces the intensity of absorption in the IR region; secondly, the (R absorption band tends to tail into the visible region, producing highly coloured compounds.
  • Dendrimetv for example, are useful for exerting maximum stenc repulsion since they have a plurality of branched chains, such as polymeric chains.
  • any raolery or group that can interfere sufficiently with the cofacial ⁇ - ⁇ interactions of adjacent dye molecules will be suitable for minimizing visible absorption.
  • a 1 may be selected to add further hydropniliciry to the dye molecule to increase its water-dispersibility.
  • the napbtbalocvanine dyes according to the present invention are synthesized via a cascaded coupling of four 2,3-dlcyaoonapthalene (1) molecules, although they may also be prepared from the corresponding 1-amino-3-iminoisoindolene (2).
  • the cascaded base-catalysed macrocycusation may be facilitated by metal templating, or it may proceed In the absence of a metal. If macrocylisanon it performed in the absence of a lempla ⁇ ng metal, then a metal may be readily inserted into the resultant metal-free napthalocyanine. Subsequent sulfonation and salt formation proceed by standard procedures. Further synthetic details are provided below in the Examples.
  • hydrocarbyl is used herein to refer to monovalent groups consisting generally of carbon and hydrogen. Hydrocarbyl groups thus include alkyl, alkenyl and alkynyl groups (in both straight and branched chain forms), carbocycuc groups (including polycycloalkyl groups such as bicyclooctyl and adamantyl) and aryl groups, and combinations of the foregoing, such as alkylcycloalkyl, alkylpolycycloalkyl, alkylaryl, alkenyUryl, alkvnylaryl, cycloalkylaryl and cycloalkenylaryl groups.
  • bydrocarbylene refers to divalent groups corresponding to the monovalent hydrocarbyl groups described above. Unless specifically stated otherwise, up to four -C-C- and/or -C-H moieties in the hydrocarbyl group may be optionally interrupted by one or more moieties selected from -O-; -NR"-; -S-; -C(O)-; -C(O)O-; -C(O)NR"-; -S(O)-; -SO 2 -; -SO 2 O-; -SOjNR 1 "-; where R* is ⁇ group selected from H, C M1 alky], C 6 ., 2 aryl or C 6 - I2 arylalkyl.
  • the terra "hydrocarbyl" may include moieties such as heteroaryl, ether, thioetfaer, carboxy, hydroxy I, alkoxy, amine, thiol, amide, ester, ketone, sulfoxide, sulfonate, sulfonamide etc.
  • the hydrocarbyl group ruay comprise up to four subsdtuents independently selected from halogen, cyano, nitro, a hydroptulic group aa defined above (e.g. -SOjH, -SOjK, -CO 2 Na, -NH 3 * , -NMe/ etc.) or a polymeric group as defined above (e g a polymeric group derived from polyethylene glycol).
  • aryl is used herein to refer to an aromatic group, such as phenyl, naphthyl or oriprycenyl. Ci-it aryl, for example, refers to an aromatic group having from 6 to 12 carbon atoms, excluding any subs ⁇ cueDts.
  • aryiene refers to divalent groups corresponding to the monovalent aryl groups described above. Any reference to aryl implicitly includes aryiene, where appropriate.
  • heteroaryl refers to an aryl group, where 1 , 2, 3 or 4 carbon atoms are replaced by a heteroatom selected from N, O or S.
  • heteroaryl (or heteroarora ⁇ tic) groups include pyridyl, benzin ⁇ dazolyl, indazolyl, quinolinyl, isoquinolinyl, indoUnyl, isoindolinyl, indolyl, ⁇ oindolyl, ruranyl, ihiophenyl, pyrrolyl, thlazoly), imidazotyl, oxaiolyl, isoxazolyl, pyrazolyl, isoxazolonyl, piperazinyl, pyrimidLnyl, piperidinyl morphollnyl, pyrrolidinyl, ⁇ othiazolyl, triazolyl, oxadiazolyl, tbiadiazoly
  • heteroarylene refers to divalent groups corresponding to the monovalent heteroaryl groups described above. Any reference to beteroaryt implicitly includes beteroarylene, where appropriate. Unless specifically stated otherwise, aryl, aryiene, beteroaryl and beteroarylene groups may be optionally substituted with 1 , 2, 3, 4 or 5 of the substitueius described below.
  • the optional subsuruenr(9) are independently selected from C t4 j alkyl, C 1 - 3 alkoxy, -(OCH.CH ⁇ OR 1 * (wherein d ifl an integer from 2 to 5000 and K J U H, C 14 alkyl or C(O)C 1 .* alkyl), cyano, halogen, amino, hydroxyl, thiol, -SR', -NR"R V , nitro, phenyl, phenoxy, -CO 2 R', -C(O)R', -OCOR".
  • R" and R' are independently selected from hydrogen, Ci.u alky), phenyl or pheny
  • R" or R' groups may be substituted with three subsoruenrs: - SO 2 NHPh. -CO 2 Me croup and -NH 2 .
  • alley r is used herein to refer to alkyl groups in both straight and branched forms,
  • the alkyl group may be interrupted with 1 , 2 or 3 heteroatoras selected from O, N or S.
  • the alkyl group may also be interrupted with 1 , 2 or 3 double and/or triple bonds.
  • the term “alkyl” usually refers to alkyl groups having no heteroatom interruptions or double or triple bond interruptions.
  • alkenyl groups are specifically mentioned, this is not mieoded to be construed as a limitation on the definition of "alkyl” above.
  • alky) also includes balogenoalkyl groups.
  • a C,. n alkyl group may.
  • alkyl group may contain any one or more of the following groups: ibe group -OC(O)CM 2 aUO'l specifically includes -OC(O)CF 3 .
  • alkyl group may contain any one or more of the following groups:
  • any reference to "alley)" means C
  • alkyl also includes cycloalkyl groups.
  • cycloelkyl includes cyclo ⁇ tkyl, polycycloalkyl, and cycloalk ⁇ ny) groups, as well as combinations of these with linear alkyl groups, such as cycloalkylalky) groups.
  • the cycloalkyl group may be interrupted with 1 , 2 or 3 bete ⁇ oatoms selected from O, N or S.
  • the term “cycloalkyl” usually refers to cycloalkyl groups having no heteroatom interruptions. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cyclohexenyl, cyclohexylmeihyl and adamancyl groups.
  • arylalkyt refers to groups such aa benzyl, phenylethyl and naphihylmetbyl.
  • halogen or “halo” is used herein to refer to any of fluorine, chlorine, bromine and iodine.
  • halogen refers to chlorine or fluorine substituents.
  • substituent io question may consist entirely or partially of the group specified.
  • a substituent comprising an acid group (including salts thereof) may be of formula - ⁇ CH ⁇ J -SOJK, wherein j is O or an integer from 1 to 6.
  • substituted may be, for example, an alkyl group, which has a specified group attached.
  • the present invention also provides an inkjet ink.
  • the inkjet ink is a water-baaed inkjet ink.
  • Water-based inkjet ink compositions are we U known in the literature and, is addition to water, may comprise additives, such as co-solvents, biocides, sequestering agents, bumectants, viscosity modifiers, penetrants, wetting agents, surfactants etc.
  • Co-solvents are typically water-soluble organic solvents.
  • Suitable water-soluble organic solvents include C 1-4 alkyl alcohols, sucb as ethanol, methanol, butanoL, propanol, and 2-propanol, glycol ethers, sucb as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol raono-isopropyl ether, diethylene glycol mono- isopropyl ether, ethylene glycol mono-n-butyl etheT, dieihylene glycol mono-n-butyl ether, methylene glycol t ⁇ oDo-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t
  • water-soluble organic solvents include polar solvents, such as 2-pyrrolidone, N- methylpyrrolidone, ⁇ -caprolacram, dimethyl sulfoxide, sulfolane, morpholine, N-etbylr ⁇ orpholine, 1-3- dimetbyl-2-imjdA- ⁇ lidu ⁇ me and combination- thereof.
  • the InkJet ink may contain a high-boiling water-soluble organic solvent which can serve as a wetting agent or humectant for imparting water rcten ⁇ vity and wetting properties to the ink composition.
  • a high-boiling water-soluble organic solvent includes one having a boiling point of 180°C or higher.
  • water-soluble organic solvent having a boiling point of 180°C or higher examples include ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene- 1 ,4-diol, 2-ethyt- 13-hexaned ⁇ ol, 2-methyl-2,4-pentanediol, tripropylene glycol monoraethyl ether, dipropylene glycol monoethyl glycol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, triethylene glycol monomethyl ether, te ⁇ aethylene glycol, methylene glycol, dietbylcne glycol monoburyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, tripropylene glycol, polyethylene glycols having molecular weights of 2000 or lower, 1 ,3 -propylene glycol, isopropylene
  • the total water-soluble organic solvent content in the inkjet ink is preferably about 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total ink composition.
  • Suitable wetting agents or bumectants include saccharides (including monosaccharides, oligosaccharides and polysaccharides) and derivatives thereof (e.g. malotol, sorbitol, xyLttol, hyaluronic salts, aldonic acids, uronic acids etc.)
  • the inkjet ink may also contain a penetrant for accelerating penetration of the aqueous ink into the recording medium.
  • Suitable penetrants include pojyhydric alcohol alkyl ethers (glycol ethers) and/or 1 ,2- alkyldiok
  • suitable polyhydric alcohol alkyl ethers are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono-n-propyl emer, ethylene glycol monc-isopropyl ether, dietbylene glycol mono-isopropyl ether, ethylene glycol mouo- D-buryl ether, diethylene glycol mono-n-butyl ether, methylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether,
  • Examples of suitable 1 ,2-alkyldiols are 1,2-pentanediol and 1 ,2-hexaoediol.
  • the penetraiu may also be selected from straight-chain hydrocarbon diols, such as 13-propanediol, 1,4-b ⁇ uanedioL, 1 ,5-pentanediol. 1 ,6-hexanediol, 1,7-beptanediol, and 1,8-ocranediol.
  • Glycerol or urea may also be used as penetrants.
  • the amount of penetrant is preferably in the range of l to 20% by weight, more preferably 1 to 10% by weight, based on the total ink composition.
  • the inkjet ink may also contain a surface active agent, especially an anionic surface active agent and/or a noniooic surface active agent.
  • a surface active agent especially an anionic surface active agent and/or a noniooic surface active agent.
  • useful anionic surface active agents include sulfonic acid types, such as alkanesulibnic acid salts, ⁇ -olefinsulfouic acid salts, alkylbenzenesulfonic acid salts, alkylnapbthale ⁇ esuUbnic acids, acylmethyltaurines, and dialkyisulfosuccinic acids; alkylsuLforic ester salts, sulfated oils, sulfated olefins, polyoxyetbylene alkyl ether sulfurio ester salts; carboxyUc acid types, e.g., fatty acid salts and alkylsarcostne salts, and phosphoric acid ester types, such as
  • Suitable non ionic surface active agents include ethylene oxide adduct types, such as polyoxyetbylcne alkyl ether ⁇ , polyoxyethyleue alkylphenyl ethers, polyoxyethyl ⁇ oe alkyl esters, and polyoxyethylene aUcylamides; polyol eater types, such as glycerol alkyl esters, sorbitan alkyl esters, and sugar alkyl esters; polyeiber types, such as polyhydric alcohol alky) ethers; and alkanoUnude types, such as alkanolamine (airy acid amides.
  • ethylene oxide adduct types such as polyoxyetbylcne alkyl ether ⁇ , polyoxyethyleue alkylphenyl ethers, polyoxyethyl ⁇ oe alkyl esters, and polyoxyethylene aUcylamides
  • polyol eater types such as glycerol alkyl est
  • nonionic surface active agents are ethers such a ⁇ polyoxyethylene nonylphenyl ether, polyoxyetbylene octylphenyl eiher, polyoxyethylene dodccylphenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyalkylene alkyl ethers (e.g. polyoxyetbylene alky) ethers); and esters, such as polyoxyethylene oleate, polyoxyethylene oleate ester, polyoxyethylene distearate, sorbitao laurate.
  • ethers such as polyoxyethylene nonylphenyl ether, polyoxyetbylene octylphenyl eiher, polyoxyethylene dodccylphenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyalkylene alky
  • Acetylene glycol surfece active agents such as l ⁇ J ⁇ -ietramethyl-5-decyne ⁇ J-diol, 3,6-dunethyN4-octyne-3,6-diol or 3,S-dimethyl-1-hexvn-3-ol. may also be used
  • the inkjet ink may also include a biocide.
  • a biocide such as benzoic acid, dichloropbene, hexachlorophene, sorbic acid, bydroxybenzoic esters, sodium dehydroacetate, 1 -2-benthiazolu>3-onfl, 3,4>isothiazolin-3-ooe or 4,4-dimethyloxazolidine.
  • the inkjet ink may also contain a sequestering agent, such as emylenediamineietraacetic acid (EDTA).
  • EDTA emylenediamineietraacetic acid
  • the inkjet ink may also contain a singlet oxygen quencher.
  • the presence of singlet oxygen quenche ⁇ (s) in the ink reduces the propensity for the tR-absorbing dye to degrade.
  • the quencher consumes any singlet oxygen generated in the vicinity of the dye molecules and, hence, minimizes iheir degradation.
  • An excels of singlet oxygen quencher is advantageous for minimizing degradation of the dye and retaining its JR-absorbing properties over time.
  • the singlet oxygen quencher is selected from ascorbic acid, 1,4-diazabicyclo-[2.2.2]ocrane (DABCO), azides (eg. sodium azide), histidin ⁇ or tryptophan.
  • the present invention also provides an inkjet printer comprising a printhead in fluid communication with at least one ink reservoir, wherein said ink reservoir comprises an inkjet ink as described above.
  • InkJet printers such as thermal bubble-jet and piezoelectric printers, are well known in the art and will form part of the skilled person's common general knowledge.
  • the printer may be a high-speed inkjet printer.
  • the printer is preferably a pagewidth prinier.
  • Preferred inkjet printers and printheads for use in che present invention are described in the following patent applications, all of which are incorporated herein by reference in their entirety.
  • a rvfemjet printer generally has two printhead integrated circuits that are mounted adjacent each other to fomi a pagewidth printhead.
  • the printbead ICs can vary in size from 2 inches to 8 inches, so several combinations can be used to produce, say, an A4 pagewidth printhead.
  • two printhead ICs of 7 and 3 inches, 2 and 4 inches, or S and 5 inches could be used to create an A4 printhead (the notation is 7:3).
  • 6 and 4 (6:4) or 5 and 5 (5:5) combinations can be used.
  • An A3 printhead can be constructed from 8 and 6-incb printhead integrated circuits, for example.
  • a single princh&ad integrated circuit, or more than two such circuits can also be used to achieve (be required printbead width.
  • a preferred prinmead embodiment of the pinthead will now be described with reference to Figures
  • a printhead 420 takes the form of an elongate unit.
  • the components of the printbead 420 include a support member 421 , a flexible PCB 422, an ink distribution molding 423, an ink distribution plate 424, a MEMS printhead comprising first and second printhead integrated circuits OCs) 425 and 426, and busbars 427.
  • the support member 421 is can be formed from any suitable material, such aa metal or plastic, and can be extruded, molded or formed in any other way.
  • the support member 421 should be strong enough TO hold the other components in the appropriate alignment relative to each other whilst stiffening and strengthening the printhead as a whole.
  • the flexible PCB extends the length of the printhead 420 and includes first and second electrical connectors 428 and 429.
  • the electrical connectors 428 and 429 correspond with flexible connectors (not shown).
  • the electrical connectors include contact areas 450 and 460 that, in use, are positioned in contact with corresponding output connectors from a SoPEC chip (not shown). Data from the SoPEC chip posses along the electrical connectors 428 and 429, and is distributed to respective ends of the fust and ⁇ econd printhead ICs 425 and 426.
  • the ink distribution molding 423 includes a plurality of elongate conduits
  • the distribution plate 424 is a multi-layer construction configured to take fluids provided locally from the fluid apertures 431 and distribute them through smaller distribution apertures 432 into the pnnthead ICs 425 and 426 (as shown in Figure 20).
  • the printhead ICs 425 and 426 are positioned end to end, and are held in contact with the distribution plate 424 so that ink from the smaller distribution apertures 432 can be fed into corresponding apertures (not shown) in the printhead ICs 425 and 426.
  • the busbars 427 are relatively high-capacity conductors positioned to provide drive current to the actuators of the printhead nozzles (described in detail below). As best shown in Figure 20, the busbars 427 are retained in pom-ion at one end by a socket 433, and at both ends by wrap-around wings 434 of the flexible PCB 422. The busbars also help hold the printhead ICs 425 in position. As shown best in Figure 18, when assembled, the flexible PCB 422 is effectively wrapped around the other components, thereby holding them in contact with each other. Notwithstanding this binding effect, the support member 421 provides a major proportion of the required 9tifihes ⁇ and strength of the printhead 420 as a whole.
  • thermo bend actuator and "bubble forming heater element actuator”
  • thermal bend actuator there is typically provided a nozzle arrangement having a nozzle chamber containing ink and a thermal bend actuator connected to a paddle positioned within the chamber.
  • the thermal actuator device is actuated so as to eject ink from the nozzle chamber.
  • the preferred embodiment includes a particular thermal bend actuator which includes a series of tapered portions for providing conductive hearing of a conductive (race.
  • the actuator is connected to the paddle via an arm received through a slotted wall of the nozzle chamber.
  • the actuator arm has a mating shape so as to mate substantially with the surfaces of the slot in the nozzle chamber wall.
  • a nozzle chamber 501 is provided filled with ink S02 by means of an ink inlet channel 503 which can be etched through a wafer substrate on which the nozzle chamber 501 rests.
  • the nozzle chamber S0 I further includes an ink ejection port 504 around which an Ink meniscus forms.
  • a paddle type device 507 which is interconnected to an actuator
  • the actuator 508 includes a beater means e.g. 509 located adjacent to an end portion of a post 510.
  • the post 510 is fixed to a substrate.
  • the heater means 509 is heated so as to undergo thermal expansion.
  • the beater means 509 itself or the other portions of the actuator 508 are built from materials having a high bend efficiency where the bend efficiency is defined as:
  • a suitable material for the boater elements U a copper nickel alloy which can be formed so as to bend a glass material.
  • the beater means 509 is ideally located adjacent the end portion of the poet 510 such that (be effects of activation are magnified at the paddle end S07 such that small thermal expansions near the post 5 I0 result in large movements of the paddle end.
  • the beater means 509 and consequential paddle movement causes a general increase in pressure around the ink meniscus 505 which expands, as illustrated in Figure 22 ⁇ b), in a rapid manner
  • the beater current is pulsed and ink is ejected out of the port 504 in addition to flowing in from the ink channel 503.
  • the paddle 507 is deactivated to again return to its quiescent po ⁇ iu ' on.
  • the deactivation causes a general reflow of the ink into the nozzle chamber.
  • the forward momentum of the ink outside the nozzle rim and the corresponding backflow results in a general necking and breaking off of the drop 512 which proceeds to the print media.
  • the collapsed meni ⁇ ous 505 results in a general sucking of ink into the nozzle chamber 502 via tbe ink flow channel 503.
  • me nozzle chamber 501 is refilled such that tbe position in Figure 22(a) U again reached and the nozzle chamber is subsequently ready for the ejection of another drop of ink.
  • Figure 23 illustrates a side perspective view of the nozzle arrangement.
  • Figure 24 illustrates sectional view through an array of nozzle arrangement of Figure 23.
  • the actuator 508 includes a series of tapered actuator units e.g. 515 which comprise an upper glass portion (amorphous silicon dioxide) 516 formed on top of a titanium nitride layer 517.
  • a copper nickel alloy layer hereinafter called cupronickel
  • cupronickel a copper nickel alloy layer
  • Tbe titanium nitride layer 517 is in a tapered form and, as such, resistive hearing takes place near an end portion of the post 510.
  • Adjacent titanium nitride/glass portions 51S are interconnected at a block portion 519 which also provides a mechanical structural support for the actuator 503.
  • the heater means 509 ideally includes a plurality of the tapered actuator unit 515 which are elongate and spaced apart such that, upon beating, tbe bending force exhibited along the axis of the actuator 508 is maximized. Slots are defined between adjacent tapered units 515 and allow for slight differential operation of each actuator 508 with respect to adjacent actuators 508.
  • the block portion 519 is interconnected to an arm 520.
  • Tbe arm 520 is in turn connected to the paddle 507 inside the nozzle chamber 501 by means of a slot e.g. 522 formed in the side of the nozzle chamber 501.
  • Tbe slot 522 ia designed generally to mate with the surfaces of the arm 520 so as to minimize opportunities for the outflow of ink around the arm 520.
  • the ink is held generally within the nozzle chamber 501 via surface tension effects around the slot 522.
  • a conductive current is passed through the titanium nitride layer 5)7 via viae within the block portion 519 connecting to a lower CMOS layer 506 which provides tbe necessary power and control circuitry for the nozzle arrangement.
  • the conductive current results in beating of the nitnde layer 517 adjacent to the post 510 which results in a general upward bending of the arm 20 and consequential ejection of ink out of the nozzle 504.
  • the ejected drop is printed on a page in the usual manner for an inkjet printer as previously described.
  • Aa array of nozzle arrangements can be formed so as to create a single printhead.
  • Figure 24 there is illustrated a partly sectioned various array view which comprises multiple ink ejection nozzle arrangements of Figure 23 laid out in interleaved lines so as to form a priotbead array.
  • different types of arrays can be formulated including nil I color arrays etc.
  • the unit cell 1001 of a bubble forming heater element actuator comprises a nozzle plate 1002 with nozzles 1003 therein, the nozzlea having nozzle rims 1004, and apertures 1005 extending through the nozzle plate.
  • the nozzle plate 1002 is plasma etched from a silicon nitride structure which is deposited, by way of chemical vapor deposition (CVD), over a sacrificial material which is subsequently etched.
  • CVD chemical vapor deposition
  • the prinrhead also includes, with respect to each nozzle 1003, side walls 1006 on which the nozzle plate is supported, a chamber 1007 defined by the walls and the nozzle plate 1002, a multi-layer substrate 1006 and an inlet passage 1009 extending through the multi-layer substrate to the far side (not shown) of the substrate.
  • a looped, elongate heater element 1010 is suspended within the chamber 1007, so that the element is in the form of a suspended beam.
  • the pnnthead as shown is a raicroeleciromechanical system (MEMS) structure, which is formed by a lithographic process.
  • MEMS raicroeleciromechanical system
  • ink IOU from a reservoir enters the chamber 1007 via the inlet passage 1009, so that the chamber fills. Thereafter, the heater element 1010 is heated for somewhat less than 1 micro second, 9o that the beating is in the form of a thermal pulse. It will be appreciated that the beater element 1010 is in thermal contact with the ink 1011 in the chamber 1007 60 that when the element is heated, this causes the generation of vapor bubbles in the ink. Accordingly, the ink 101 1 constitutes a bubble forming liquid.
  • the bubble 1012 once generated, causes an increase in pressure within the chamber 1007, which in turn causes the ejection of a drop 1016 of the ink 10) 1 through the nozzle 1003.
  • the rim 1004 assists in directing the drop 1016 as it is ejected, so as to minimize the chance of a drop misdirection.
  • the increase in pressure within the chamber 1007 not only pushes ink 1011 out through the nozzle 1003, buc also pushes some ink back through the inlet passage 1009.
  • the inlet passage 1009 i ⁇ approximately 200 to 300 microns in length, and is only approximately 16 microtis in diameter. Hence there is a substantial viscous drag. A9 a result, the predominant effect of the pressure rise in the chamber 1007 is to force ink out through the nozzle 1003 as an ejected drop 1016, rather than back through the inlet passage 9.
  • the ink drop 1016 is being ejected is shown during its "necking phase" before the drop breaks off.
  • the bubble 1012 has already reached its mavimnm size and has then begun to collapse towards the point of collapse 1017.
  • the collapsing of the bubble 1012 towards the point of collapse 1017 causes some Ink 1011 to be drawn from within the nozzle 1003 (from the sides 1018 of the drop), and some to be drawn from the inlet passage 1009, towards the point of collapse. Most of the ink 1011 drawn in this manner is drawn from the nozzle 1003. forming an annular neck I Ol 9 at the base of the drop 16 prior to its breaking off.
  • the drop 1016 requires a certain amount of momentum to overcome surface tension forces, in order to break off.
  • the diameter of the neck 10)9 reduces thereby reducing the amount of total surface tension holding the drop, so that the momentum of the drop as it is ejected out of the nozzle is sufficient to allow the drop to break off.
  • the present invention also provides an inkjet ink cartridge comprising an inkjet ink as described above.
  • Ink cartridges for inkjet printers are well known in the art and are available in numerous forms.
  • the inkjet ink cartridges of the present invention are replaceable.
  • InkJet cartridges suitable for use in the present invention are described in the following patent applications, all of which are incorporated herein by reference in their entirety.
  • the ink cartridge comprises: a housing defining a plurality of storage areas wherein at least one of the storage areas contains colorant for printing information that is visible to the human eye and at least one of the other storage areas contains an inkjet ink as described above.
  • each storage ansa is sized corresponding to the expected levels of use of its contents relative to the intended print coverage for a number of printed pages.
  • Figure 12 shows the complete assembly of the replaceable ink cartridge 627. It has bladders or chambers for storing fixative 644, adhesive 630, and cyan 631. magenta 632, yellow 633, black 634 and infrared 635 inks.
  • the cartridge 627 also contains a micro air Oiler 636 in a base molding 637. As shown in Figure 9, the micro air filler 636 interfaces with an air pump 638 inside the printer via a hose 639. This provides filtered air to the printheads 70S to prevent ingress of micro particles into the MemjetTM printheads 705 which may clog the nozzles.
  • the operational life of the filter is effectively linked to the life of the cartridge. This ensures that the filter is replaced together with die cartridge rather then relying on the user to clean or replace the filter at the required intervals. Furthermore, the adhesive and infrared ink are replenished together with the visible inks and air filter thereby reducing how frequently me printer operation i ⁇ interrupted because of the depletion of a consumable material.
  • the cartridge 627 has a thin wall casing 640.
  • the ink bladders 631 to 63 S and fixitive bladder 644 are suspended within the casing by a pin 645 which books the cartridge together.
  • the single glue bladder 630 is accommodated in tb « base molding 637. This is a folly recyclable product with a capacity for printing and gluing 3000 pages (1500 sheets).
  • the dyes of the present invention are especially suitable for use in
  • HyperlabelTM and neipage systems Such systems are described in more detail below and in the patent applications listed above, all of which are incorporated herein by reference in their entirety.
  • the present invention provides a substrate having an IR-absorbing dye as described above disposed thereon.
  • the substrate comprises an interface surface.
  • the dye is disposed in the form of coded data suitable for use in netpage and/or HyperlabelTM systems.
  • the coded data may be indicative of the identity of a product item.
  • the coded data is disposed over a substantial portion of an interface surface of the substrate (e.g. greater man 20%, greater than 50% or greater than 90% of the surface).
  • the substrate is IR reflective so that the dye disposed thereon may be detected by a sensing device.
  • the substrate may be comprised of any suitable material such as plastics (e g polyolefin ⁇ , polyesters, polyamides etc.), paper, metal or combinations thereof.
  • the substrate is preferably a paper sheet.
  • the substrate is preferably a tag, a label, a packaging material or a surface of a product item
  • tags and labels are comprised of plasties, paper or combinations thereof.
  • the substrate may be an interactive product item adapted for interaction with a user via a sensing device and a computer system, the interactive product item comprising: a product item having an identity; an interface surface associated with the product item and having disposed thereon information relating to the product item and coded data indicative of the identity of the product item, wherein said coded data comprise an IR-absorbing dye as described above.
  • Netpage applications of this invention are described generally in the sixth and ⁇ eventh aspects of the invention above.
  • HyperlabelTM applications of this invention are described generally in the eighth and ninth aspects of the invention ⁇ bovc.
  • the preferred form of the netpage system employs a computer interface in the form of a mapped surface, that is, a physical surface wbicb contains references to a map of the surface maintained in a computer system.
  • the map references can be queried by an appropriate sensing device.
  • the map references may be encoded visibly or inv ⁇ ibly, and defined La such a way that a local query oo the mapped surface yields an unambiguous map reference both within the map and among different maps.
  • the computer system can contain information about features on the mapped surface, and such information can be retrieved based on map references supplied by a sensing device used with the mapped surface. The information thus retrieved can take the form of actions which are initialed by the computer system on behalf of the operator in response to the operator's interaction with the surface features.
  • the netpage system relies on the production of, and human interaction with, netpages. These are pages of text, graphics and images printed on ordinary papor, but which work like interactive web pages. Information is encoded on each page using ink which is substantially invisible to the unaided human eye. The ink, however, and thereby the coded data, can be sensed by an optically imaging pen and transmitted to the netpage system.
  • buttons and hyperlinks on each page can be clicked with the pen to request ioformatioo from the network or to signal preferences to a network server.
  • text written by hand on a netpage is automatically recognized and converted to computer text in the netpage system, allowing forms to be filled in.
  • signatures recorded on a netpage are automatically verified, allowing e-conuaerce transactions to be securely authorized.
  • a printed netpage 1 can represent an interactive form which can be filled in by the user both physically, on the printed page, and "electronically", via communication between the pen and the netpage system.
  • the example shows a "Request” form containing name and address fields and a submit button.
  • the netpage consists of graphic data 2 printed using visible ink, and coded data 3 printed as a collection of rags 4 using invisible ink.
  • the corresponding page description 5, stored on the netpage network describes the individual elements of the netpage. In particular it describes the type and spatial extern (zone) of each interactive element (i.e. text field or burton in the example), to allow the netpage system to correctly interpret input vie the netpage.
  • the submit button 6, for example has a zone 7 which corresponds to the spatial extent of the corresponding graphic 8.
  • the netpage pen 101 works in conjunction with a personal computer (PC), Web terminal 75, or a netpage printer 601.
  • the netpage printer ⁇ an Interne t-co ⁇ oec ted printing appliance for home, office or mobile use.
  • the pen is wireless and communicates securely with toe nerpage network via a short-range radio link 9.
  • Short-range communication is relayed to the netpage network by a local relay function which is cither embedded in the PC, Web terminal or nctpace printer, or is provided by a separate relay device 44.
  • the relay function can also be provided by a mobile phone or other device which incorporates botb short-range and longer-range communications functions.
  • the netpage pen utilises a wired connection, such as a USB or other serial connection, to the PC, Web terminal, netpage printer or relay device.
  • a wired connection such as a USB or other serial connection
  • the netpage printer 601 is able to deliver, periodically or on demand, personalized newspapers, magazines, catalogs, brochures and other publications, all printed at high quality as interactive netpages.
  • the nerpage printer is an appliance which can be, for example, wall-mounted adjacent to an area where the morning news is first consumed, such as in a user's kitchen, near a breakfast table, or near the household's point of departure for the day. It also comes in tabletop, desktop, portable and miniature versions.
  • Neipage ⁇ printed at their point of consumption combine the ados of paper with the timeliness and interactivity of an interactive medium.
  • the netpage pen 101 interacts with the coded data oo a printed netpage 1 (or product item 201) and communicates the interaction via a short-range radio link 9 to a relay.
  • the relay sends the interaction to the relevant netpage page server 10 for interpretation.
  • the page server sends a corresponding message to application computer software running on a netpage application server 13.
  • the application server may in turn send a response which is printed on the originating printer.
  • the PC, Web terminal, netpage printer or relay device may communicate directly with local or remote application software, including a local or remote Web server Rclatedly, output is not limited to being printed by the netpage printer. It can also be displayed on the PC or Web terminal, and further interaction can be screen-based rather than paper-based, or a mixture of the two.
  • the Qctpagc system is made considerably more convenient in the preferred embodiment by being used in conjunction with high-speed roicroelectromechanjcal system (MEMS) based inkj ⁇ t (MemjetTM) printers. In the preferred form of this technology, relatively high-speed and high-quality printing is made more affordable to consumers.
  • a netpage publication has the physical characteristics of a traditional newsmagazine, such as a set of letter-size glossy pages printed in full color on bom sides, bound together for easy navigation and comfortable handling.
  • the netpage printer exploits the growing availability of broadband Internet access. Cable service is available to 95% of households in the United States, and cable modem service offering broadband Internet access is already available to 20% of these.
  • the netpage printer can also operate with slower connections, but with longer delivery times and lower image quality. Indeed, the netpage system can be enabled using existing consumer inkjet and laser printen., although the system will operate more slowly and will therefore be les ⁇ acceptable from a consumer's poiot of view.
  • the netpage system is hosted oo a private intranet.
  • the netpage system is boated on a single computer or computer-enabled device, such as a printer.
  • Netpage publication servers 14 on the netpage network are configured to deliver print-quality publications to netpage printer.
  • Periodical publications are delivered automatically to subscribing netpage printers via pointcasting and multicasting Internet protocols.
  • Personalized publications are filtered and formatted according to individual user profiles.
  • a oetpage printer can be configured to support any number of pens, and a pen can work with any number of netpage printers.
  • each netpage, pen has a unique identifier.
  • a household may have a collection of colored netpage pens, one assigned to each member of the family. This allows each user to maintain a distinct profile with respect to a netpage publication server or application server.
  • a netpage pen con also be registered with a netpage registration server 11 and linked to one or more payment card accounts. This allows e-commerce payments to be securely authorized using the netpage pea
  • the netpage registration server compares the signature captured by the netpage pen with a previously registered signature, allowing it to authenticate the user's identity to an e-commerce server. Other biometrics can also be used to verily identify.
  • a version of the nerpage pen includes fingerprint scanning, verified in a similar way by the oetpage registration server.
  • a oetpage primer may deliver periodicals such as the morning newspaper without user intervention, it can be configured never to deliver unsolicited junk mail. In its preferred form, it only delivers periodicals from subscribed or otherwise authorized sources.
  • the netpage printer is unlike a fax machine or e-mail account which is visible to any junk mailer who knows the telephone number or email address.
  • UML Unified Modeling Language
  • a class diagram consists of a set of object classes connected by relationship:), and two kinds of relationships are of interest here: associations and generalizations.
  • Ae association represents some kind of relationship between objects, ie. between instances of classes.
  • a generalization relates actual classes, and can be understood in the following way. if a class ⁇ $ thought of as the set of all objects of that class, and class
  • A is a geueralizaoon of class B, then B is simply a subset of A.
  • the UML does not directly support second- order modelling - i.e. classes of classes.
  • Each class is drawn as a rectangle labelled with the name of the class. It contains a list of the attributes of the class, separated from the name by a horizontal line, and a list of the operations of the class, separated from the attribute list by a horizontal line. In the class diagrams which follow, however, operations are never modelled.
  • An association u drawn as a line joining two classes, optionally labelled at either end with the multiplicity of the association. The default multiplicity is o ⁇ e.
  • An asterisk (*) indicates a multiplicity of
  • Each association is optionally labelled with its name, and is also optionally labelled at either end with the role of the corresponding class.
  • An open diamond indicates an aggregation association ("is-part-of '), and is drawn at the aggregator end of the association line.
  • a generalization relationship (“is-a") is drawn as a solid line joining two classes, with an arrow
  • Netpages are the foundation on which a neipage network is built. They provide a paper-based user interface to published information and interactive services.
  • a netpage consists of a printed page (or other surface region) invisibly tagged with references to an online description of me page.
  • the online page description is maintained persistently by a netpage page server.
  • the page description describes the visible layout and content of the page, including text, graphics and images. It also describes the input elements on the page, including burtons, hyperlinks, and input fields.
  • a netpage allows markings made with a netpage pen on its surface to be simultaneously captured and processed by the netpage system.
  • each netpage is assigned a unique page identifier. This page ID has sufficient precision to distinguish between a very large number of netpages.
  • Each reference to the page description is encoded in a printed tag. The tag identifies the unique page on which it appears, and thereby indirectly ideo ⁇ fies the page description. The tig also identifies its own position on the page. Characteristics of the tags are described in more detail below
  • Tags are printed in infrared-absorptive ink on any substrate which is infrared-reflective, such as ordinary paper. Near-infrared wavelengths are invisible to the human eye but are easily sensed by a solid- state image sensor with an appropriate filter.
  • a tag is sensed by an area image censor in the netpage pen, and the tag data is transmitted to the ne ⁇ age system via the nearest netpage printer.
  • the pen is wireless and communicates with the netpage printer via a short-range radio link.
  • Tags are sufficiently small and densely arranged that the pen can reliably image at least one tag even on a single click on the page. It is important that the pen recognize the page IO and position on every interaction with the page, since the interaction is stateless. Tags are error-correctably encoded to make them partially tolerant to surface damage.
  • the netpage page server m ⁇ nmin g a unique page instance for each printed oetpage, allowing it to maintain a distinct set of user-supplied values for input fields in the page description for each printed netpage.
  • Tbe primed netpage may be part of a printed netpage document 45.
  • the page instance is associated with both the ⁇ etpage print ⁇ r which printed it and, if known, the netpage user who requested it.
  • one or more nctpages may also be associated with a physical object such as a product item, for example when printed onto the product item's label, packaging, or actual surface.
  • a physical object such as a product item
  • a product item for example when printed onto the product item's label, packaging, or actual surface.
  • each tag identifies the region in which it appears, and tbe location of that tag within the region
  • a tag may also contain flags which relate to tbe region as a whole or to the tag.
  • One or more flag bits may, for example, signal a tag sensing device to provide feedback indicative of a function associated with the immediate area of tbe tag, without the sensing device having to refer to a description of the region
  • a neipage pen may, for example, illuminate an "active area" LED when in the zone of a hyperlink
  • each tag contains an easily recognized invariant structure which aids initial detection, and which assists in minimizing the effect of any warp induced by tbe surface or by the sensing process.
  • the tags preferably tile the entire page, and are sufficiently small and densely arranged that the pen can reliably image at least one ug even on a single click on tbe page. It is important that the pen recognize the page ID and position on every interaction with the page, since the interaction ii stateless In a preferred embodiment, tbe region to which a rag refers coincide?
  • tbe region to which a tag refers can be an arbitrary subregion of a page or other surface. For example, it can coincide with the zone of an interactive element, in which case the region ID can directly identify the interactive element
  • each tag contains 120 bits of information.
  • the 100-bit region ID allows 2 I ⁇ W (-10 30 or a million trillion trillion) different regions to be uniquely identified.
  • the (20 bits of tag data are redundantly encoded using a (15, 5) Reed- Solomon code.
  • the (15, 5) code allows up to 5 symbol errors to be corrected per codeword, i.e. it is tolerant of a symbol error rate of up to 33% per codeword.
  • Each 4-bit symbol is represented in a spatially coherent way in the tag, and the symbols of the six codewords are interleaved spatially within the tag- This ensures that a burst error (an error affecting multiple spatially adjacent bits) damages a minimum number of symbols overall and a minimum number of symbols in any one codeword, thus maximising the likelihood that the bum error can be fully corrected.
  • Any suitable error-correctine c°de code can ⁇ e MS*d w P ⁇ 6 of a (15, 5) Reed-Solomon code, for example: a Reed-Solomon code witfa more or lees redundancy, with the same or different symbol and codeword sizes; another block code; or a different kind of code, such as a convolution ⁇ code (see, for example, Stephen B. Wicker, Error Con ⁇ ol Systems far Digital Communication and Storage, Prentice-Hall 1995, the contents of which a herein incorporated by reference thereto).
  • a Reed-Solomon code for example: a Reed-Solomon code witfa more or lees redundancy, with the same or different symbol and codeword sizes; another block code; or a different kind of code, such as a convolution ⁇ code (see, for example, Stephen B. Wicker, Error Con ⁇ ol Systems far Digital Communication and Storage, Prentice-Hall 1995, the contents of which a herein incorporated
  • the sensing device In order to support " ⁇ ingJe-click" interaction with a tagged region via a sensing device, the sensing device must be able to see at least one entire Ug in its field of view no matter where in the region or at what orientation it is positioned.
  • the required diameter of the field of view of the sensing device is therefore a function of the size and spacing of the tags.
  • Figure 5a snows a tag 4, in the form of tag 726 with four perspective targets 17.
  • the tag 726 represents sixty 4-bit Reed-Solomon symbols 747, for a total of 240 bits.
  • the tag represents each "one" bit by the presence of a mark 748, referred to as a macrodot, and each "zero" bit by the absence of the corresponding macTodot.
  • Figure 5c shows a square tiling 728 of nine tags, containing all "one" bits for illustrative purposes. It will be noted that the perspective targets are designed to be shared between adjacent tags.
  • Figure 5d shows a square tiling of 16 tags and a corresponding minimum field of view 193, which spans the diagonals of two tags.
  • Uslug a (15. 7) Reed-Solomon code, 112 bits of tag data are redundantly encoded to produce 240 encoded bits. The four codewords are interleaved spatially within the tag to maximize resilience to burst errors. Assuming ⁇ 16-bit tag ID as before, mis allows a region OD of up to 92 bite.
  • the data-bearing ⁇ iacrodoU 748 of the tag are designed to not overlap their neighbors, so that groups of tags cannot produce structures that resemble targets. This also saves ink.
  • the perspective targets allow detection of roe tag, so further targets are not required.
  • the tag may contain an orientation feature to allow disambiguation of the four possible orientations of the tag relative to the sensor
  • the present Invention is concerned with embedding orientation data in the tag data.
  • the four codewords can be arranged so that each tag orientation (in a rotational sense) contains one codeword placed at that orientation, as shown in Figure 5a, where each symbol U labelled with the number of its codeword (M) and the position of the symbol within the codeword (A-O).
  • Tag decoding then consists of decoding one codeword at each rotational orientation.
  • Each codeword can eimer contain a single bit indicating whether it is the first codeword, or rwo bits indicating which codeword it is.
  • the latter approach has che advantage that if, say, the data content of only one codeword is required, then at most two codewords need to be decoded to obtain the desired data. This may be the case if the region ID is not expected to change within a stroke and is thus only decoded at the start of a stroke. Within a stroke only the codeword containing the tag ID is then desired. Furthermore, since the rotation of the sensing device changes ⁇ lowly and predictably within a stroke, only one codeword typically needs to be decoded per frame.
  • each tag data must contain a marker pattern, and these must be redundantly encoded to allow reliable detection The overhead of such marker patterns is ⁇ imilar to the overhead of explicit perspective targets.
  • Various such schemes are described in the present applicants' co-pending PCT application PCT/ AU01/01274 filed 11 October 2001.
  • the arrangement 728 of Figure 5c shows that the square tag 726 can be used to fully tile or les ⁇ elate, i.e. without gaps or overlap, a plane of arbitrary size.
  • the tagging schemes described herein encode a single data bit using the presence or absence of a single undifferentiated macrodot, they can also u ⁇ e sets of differentiated glyphs to represent single-bit or multi-bit values, such as the sets of glyphs illustrated in the present applicants' co-pending PCT application PCT/AU01/01274 filed 11 October 2001 1.3 THE NETPAGE NETWORK
  • a netpage network consists of a distributed set of netpage page servers 10, netpage registration servers U, netpage ID servers 12, netpage application servers 13, netpage publication servers 14, Web terminals 75, ncipage primers 601 , and relay devices 44 connected via a network 19 such as the Internet, as shown in Figure 3.
  • the netpage registration server 11 is a server which records relationships between users, pens, printers, applications and publications, and thereby authorizes various network activities. It authenticates users and acts as ⁇ signing proxy on behalf of au-beocicated users in application transactions. It also provides handwriting recognition services.
  • a netpage page server 10 maintains persistent information about page descriptions and page instances.
  • the netpage network includes any number of page servers, each handling a subset of page instances. Since a page server also maintains user input values for each page instance, clients such as netpage printers send netpage input directly to the appropriate page server. The page server interprets any such input relative to the descnpbon of the corresponding page.
  • a netpage DD server 12 allocates document IDs 51 on demand, and provides load-balaocing of page servers via its ID allocation scheme.
  • a netpage printer uses the Internet Distributed Name System (DNS), or similar, to resolve a netpage page (D 50 into the network address of the 'netpage page server handling the corresponding page instance.
  • a netpage application server 13 is a server which hosts interactive netpage applications.
  • a netpage publication server 14 is an application server which publishes netpage documents to netpage printers.
  • Netpage servers can be hosted on a variety of network server platforms from manufacturers such as IBM, Hewlett-Packard, and Sun. Multiple netpage servers can run concurrently on a single host, and a single server can be distributed over a number of hosts.
  • Some or all of the functionality provided by netpage servers, and in particular the functionality provided by the [D server and the page server, can also be provided directly in a netpage appliance such a9 a netpage primer, in a computer workstation, or on a local network.
  • the netpage printer 601 is an appliance which ia registered with the netpage system and prints netpage documents on demand and via subscription. Each printer has a unique printer ID 62, and i ⁇ connected to the netpage network via a network such as the Internet, ideally via a broadband connection.
  • the netpage printer contains no persistent storage.
  • the network is the computer.
  • Netpages function interactively across space and time with toe help of the distributed neipage page servers 10, independently of particular netpage printers.
  • the netpage printer receives subscribed netpag ⁇ documents from netpage publication servers 14.
  • page layouts are typically specific to a particular subscriber and so are pointcast to the subscriber's printer via the appropriate page server.
  • Text and image objects are typically shared with other subscribers, and so are multicast to all subscribers' printers and the appropriate page servers.
  • the oetpage publication server optimizes the segmentation of document content into pointcaats and muHicasts. After receiving the pointcast of a document's page layouts, the printer knows which multicast*, if any, to listen to.
  • the printer Once the printer has received the complete page layouts and objects that define the document to be primed, it can print the document.
  • the printer rasterizes and prims odd and even pages simultaneously oo both sides of the sheet- It contains duplexed print engine controllers 760 and print engines utilizing MemjetTM printheads 350 for this purpose.
  • the printing process consists of two decoupled stages: rasterization of page descriptions, and expa ⁇ ioo and printing of page images
  • the raster image processor (IUP) consists of one or more standard
  • the duplexed print engine controllers consist of custom processors which expand, dither and print page images in real time, synchronized with the operation of the printheads in the print engines.
  • Printers not enabled for IR printing have the option to pnnt tags using IR-absorpnve black ink, although this restricts tags to otherwise empty areas of the page. Although such pages have more limited functionality than lR-printed pages, they are still classed as netpages.
  • a normal netpage printer prints netpage. on sheets of paper. More specialised netpage printers may print onto more specialised surfaced, such as globes. Each printer supports at least one surface type, and supports at least one tag tiling scheme, and hence tag map, for each surface type.
  • the tag map 8 I l which describes the tag tiling scheme actually used to print a document becomes associated with that document so that the document's tags can be correctly interpreted.
  • Figure 2 shows the netpage printer class diagram, reflecting printer-related information maintained by a registration server 1 1 on the netpag ⁇ network. 1.5 THE NETPAGE PEN
  • the active sensing device of the netpage system is typically a pen 101 , which, using its embedded controller 134, is able to capture and decode OR. position tags from a page via an image sensor
  • the image sensor is a solid-state device provided with an appropriate filter to permit sensing at only near-infrared wavelengths.
  • the system is able to sense when the nib is in contact with the surface, and the pen is able to sense tags at a sufficient rate to capture human handwriting (i.e. at 200 dpi or greater and 100 Hz or faster).
  • Information captured by the pen is encrypted and wireleasly transmitted to the printer (or base station), the printer or base station interpreting me data with respect to the (known) page structure.
  • the preferred embodiment of the netpage pen operates both as a normal marking ink pen and as a non-marking stylus.
  • the marking aspect is not necessary for using the netpage system as a browsing system, such as when it is used as an Internet interface.
  • Each netpage pen is registered with the netpage system and has a unique pen ID 61.
  • Figure 14 shows the netpage pen class diagram, reflecting pen- related information maintained by a registration server 1 1 on the netpage network.
  • the pen determines its position and orientation relative to the page.
  • the nib is attached to a force sensor, and the force on me nib is interpreted relative to a threshold to indicate whether the pen is "up” or "down".
  • This allows a interactive element on the page to be 'clicked' by pressing with the pen nib, in order to request, say, information from a network.
  • the force ⁇ captured as a continuous value to allow, say, the full dynamics of a signature to be verified.
  • the pen determines the position and orientation of its nib on the netpage by imaging, in the infrared spectrum, an area 193 of the page in the vicinity of the nib. It decodes me nearest tag and computes the position of the nib relative to the tag from the observed perspective distortion on the imaged tag and the known geometry of the pen optics. Although the position resolution of tho tag may be low, because the tag density on the page is inversely proportional to the tag size, the adjusted position resolution is quite high, exceeding the minimum resolution required for accurate handwriting recognition.
  • Pen actions relative to a netpage are captured as a series of strokes.
  • a stroke consists of a sequence of time-stamped pen positions on the page, initiated by a pen-down event and completed by the subsequent pen-up event.
  • a stroke is also tagged with the page ID 50 of the netpage whenever the page ID changes, which, under normal circumstances, is at the commencement of the stroke.
  • Each netpage pen has a current selection 826 associated with it, allowing the user to perform copy and paste operations etc.
  • the selection is timestamped to allow the system to discard it after a defined tune period.
  • the current selection describes a region of a page instance It consists of the most recent digital ink stroke captured through the pen relative to the background area of the page. It is interpreted in an application- specific manner once it is submitted to an application via a selection hyperlink acovanon
  • Each pen has a current nib 824. This is the nib last notified by the pen to the system. In the case of the default netpage pen described above, either the marking black ink cub or the non-marking stylus nib is current.
  • Each pen also has a current nib style 823. This is the nib style last associated with the pen by an application, e.g. in response to the user selecting a color from a palette.
  • the default nib style is the nib style associated with the current nib. Strokes captured through a pen are tagged with the current nib style. When the strokes are subsequently reproduced, they are reproduced in the nib style with which they are tagged.
  • the pen Whenever the pen is within range of a printer with which it can communicate, the pen slowly flashes its "online” LEO- When the pen fails to decode a stroke relative to tha page, it momentarily activates its "error” LED. When the pan succeeds in decoding a stroke relative to the page, it momentarily activates its "ok” LED.
  • a sequence of captured strokes i9 referred to as digital ink forms the basis for the digital exchange of drawings and handwriting, for online recognition of handwriting, and for online verification of signatures.
  • the pen is wireless and transmits digital ink to the netpage printer via a short-range radio link.
  • Tbe transmitted digital ink is encrypted for privacy and security and packetized lor efficient transmission, but is always flushed on a pen-up event to ensure timely handling in the printer.
  • the pen When the pen is out-of-range of a printer it buffers digital ink in internal memory, which has a capacity of over ten minutes of continuous handwriting. When the pen is once again within range of a printer, it transfers any buffered digital ink.
  • a pen can be registered with any number of printers, but because all state data resides in netpages both oo paper and on the network, it is largely immaterial which printer a pen is communicating with ai any particular tune.
  • the netpage printer 601 receives data rotating to a stroke from the pen 101 when the pen w used to interact with a netpage 1.
  • the coded data 3 of the tags 4 is read by the pen when it it used to execute a movement, such as a stroke.
  • the data allows the identity of the particular page and associated interactive element to be determined and an indication of the relative positioning of the pen relative to the page to be obtained.
  • the indicating data is transmitted to the printer, where it resolves, via the DNS, the page ID 50 of the stroke into the network address of the oetpage page server 10 which maintains the corresponding page instance 830. It then transmits the stroke to the page server. If the page was recently identified in a ⁇ earlier stroke, then tbc printer may already have the address of the relevant page server in its cache.
  • Each netpage consists of a compact page layout maintained persistently by ⁇ netpage page server (see below).
  • the page layout refers to objects such as imaged, fonts and pieces of text, typically stored elsewhere on the netpage network.
  • the page server When the page server receives the stroke from the pea, it retrieves the page description to which the stroke applied, and determines which element of the page description the stroke intersects. It is then able to interpret the stroke in the context of the type of the relevant element.
  • a “click” is a stroke where the distance and time between the pen down position and the subsequent pen up position are both less than some small maximum.
  • An object which is activated by a click typically requires a click to be activated, and accordingly, a longer stroke is ignored.
  • the failure of a pen action, such as a "sloppy" click, to register is indicated by the lack of response from the pen's "ok” LED.
  • Input through a form field can also trigger the activation of an associated hyperlink.
  • the pen generally designated by reference numeral 10l , includes a housing 102 in the form of a plastics moulding having walls 103 defining an interior space 104 for mounting the pen components.
  • the pen top 105 is J n operation rotatably mounted at one end 106 of the bo serai-transparent cover 107 is secured to the opposite end 108 of the bousing 102.
  • the cover 107 includes a F ⁇ pan 109 which substantially surrounds the end 108 of the bousing 102 and a projecting portion 110 which projects back from the main part 109 and fits within a corresponding slot 111 formed in the walls 103 of the housing 102.
  • a radio antenna 112 is mounted behind the projecting portion 110, within the housing 102.
  • Screw threads 1 13 surrounding an aperture 113A OD the cover 107 are arranged to receive a metal end piece 1 14, including corresponding screw threads 1 15.
  • the metal end piece 114 is removable to enable ink cartridge replacement.
  • the antenna 112 is also mounted on the flex PCB 117.
  • the pen can operate both as a normal marking ink pen and as a non-marking stylus.
  • An ink pen cartridge 118 with nib 119 and a stylus 120 with stylus nib 121 are mounted side by side within the housing 102. Either the ink cartridge nib 119 or the stylus nib 121 can be brought forward through open end 122 of the metal end piece 1 14, by rotation of the pen top 105.
  • Respective slider blocks 123 and 124 are mounted to the ink cartridge 118 and stylus 120, respectively.
  • a rotatable cam barrel 125 is secured to the pen top 105 in operation and arranged to rotate therewith.
  • the cam barrel 125 includes a cam 126 in the form of a slot within the walls 181 of the cam barrel Cam followers 127 and 128 projecting from slider blocks 123 and 124 fit witiun the cam 9lot 126.
  • the slider blocks 123 or 124 move relative to each other to project either the pen nib 1 19 or stylus nib 121 out through the hole 122 In the metal end piece 1 14.
  • the pen 101 has three states of operation. By turning the top 105 through 90 ⁇ steps, the three states are:
  • a second flex PCB 129 is mounted on an electronics chassis 130 which sits within the housing 102.
  • the second flex PCB 129 mounts an infrared LED 131 for providing infrared radiation for projection onto the ⁇ uriace.
  • An image sensor 132 is provided mounted on the second flex PCB 129 for receiving reflected radiation from the surface.
  • the second flex PCB 129 also mounts a radio frequency chip 133, which includes an RF transmitter and RF receiver, and a controller chip 134 for controlling operation of the pen 101.
  • An optics block 135 (formed from moulded clear plasties) sits within the cover 107 and projects an infrared beam onto the surface and receives images onto the image sensor 132.
  • Power supply wires 136 connect the components on the second flex PCB 129 to battery contacts 137 which are mounted within the cam barrel 125.
  • a terminal 138 connects to the battery contacts 137 and the cam barrel 125.
  • a three volt rechargeable battery 139 sits within the cam barrel 12S in contact with the battery contacts.
  • An induction charging coil 140 is mounted about the ⁇ econd flex PCB 129 to enable recharging of the battery 139 via induction.
  • the second flex PCB 129 also mounts an infrared LED 143 and infrared photodiode 144 for detecting displacement in tte cam barrel 125 when either (be stylus 120 or the ink cartridge 118 i ⁇ used for writing, in order to enable a determination of the force being applied to the surface by the pen nib 119 or srylus nib 121.
  • the IR pbotodiode 144 detects light from the IR LED 143 via reflectors (not shown) mounted on the slider blocks 123 and 124.
  • top 105 also includes a clip 142 for clipping the pen 101 to a pocket.
  • the pen 101 is arranged to determine the position of its nib (stylus nib 121 or ink cartridge nib 119) by imaging, in the infrared spectrum, an area of the surface in the vicinity of the nib. It records the location data from the nearest location tag, and is arranged to calculate the distance of the rub 121 or 1 19 from the location tab utilising optics 135 and controller chip 134.
  • the controller chip 134 calculates the orie ⁇ t ⁇ xion of the pen and the nib-to-tag distance from the perspective distortion observed on the imaged tag
  • the pen 101 can transmit the digital ink data (which is encrypted for security and packaged for efficient transmission) to the computing system.
  • the digital ink data is transmitted as it is formed
  • the pen 101 circuitry includes a buffer arranged to store digital ink data for approximately 12 minutes of the pen motion on the surface
  • the controller chip 134 is mounted on the second flex PCB 129 in the pen 101.
  • Figure 6 is a block diagram illustrating in more detail the architecture of the controller chip 134.
  • Figure 8 also shows representations of the RF chip 133, the image sensor 132, the tri-color status LED 116, the IR illumination T FT> 131, the IR force sensor LED 143, and the force sensor photodiode 144.
  • the pen controller chip 134 includes a controlling processor 145.
  • Bus 146 enables the exchange of data between components of the controller chip 134.
  • Flash memory 147 and a 512 KB DRAJVt 148 are also included.
  • Aa analog-to-digital converter 149 is arranged to convert the analog signal from the force seneor photodiode 144 to a digital signal.
  • An image sensor interface 152 interfaces with the image sensor 132.
  • a transceiver controller 153 and base band circuit 154 are also included to interface with the RF chip 133 which include ⁇ an RF circuit 155 and RF resonators and inductors 156 connected to (be antenna 112.
  • the controlling processor 145 captures and decodes location data from tags from the surface via the image sensor 132, monitors the force sensor photodiode 144, controls the LEDs 1 16, 131 and 143, and handles short-range radio communication via the radio transceiver 153. It is a medium-performance (-40MHz) general-purpose RISC processor.
  • the processor 145, digital transceiver components (transceiver controller 153 and baseband cirouit 154), image sensor interface 152, flash memory 147 and 512KB DRAM 14S are integrated in a single controller ASIC.
  • Analog RF components RF circuit 155 and RF resonators and inductors 1S6) are provided in the separate RF chip.
  • Tba image sensor is ⁇ CCD or CMOS image sensor. Depending oo tagging scheme, it has a size ranging from about 100x100 pixels to 200x200 pixels. Many miniature CMOS image sensors are commercially available, including the National Semiconductor LM9630.
  • the controller ASIC 134 enters a quiescent smte after a period of inactivity when the pen 101 is not in contact with a surface. Ic incorporates a dedicated circuit 150 which monitors the force sensor photodiode 144 and wakes up the controller 134 via the power manager 151 on a pen-down event.
  • the radio transceiver communicates in the unlicensed 900MHz band normally used by cordless telephones, or alternatively in the unlicensed 2.4OHz industrial, scientific and medical (ISM) band, and u ⁇ e ⁇ frequency hopping and collision detection to provide interference-free communication.
  • ISM industrial, scientific and medical
  • the pen incorporate ⁇ an Infrared Data Association (IrDA) interface for short-range communication with a base station or notpage printer.
  • IrDA Infrared Data Association
  • the pen 101 includes a pair of orthogonal ⁇ ccelerometers mounted in the normal plane of the pen 101 axis.
  • the accelerometer ⁇ 190 are shown in Figures 7 and 8 in ghost outline.
  • each location tag ID can then identify an object of interest rather than a position on the surface. For example, if the object is a user interface input element (e.g. a command button), then the tag ID of each location tag within the area of the input element can directly identify the input element.
  • a user interface input element e.g. a command button
  • the acceleration measured by the accelerometers Ln each of the x and y directions is integrated with respect to time to produce an instantaneous velocity and position.
  • the vertically-mounted netpage wallpnnter 601 is shown fully assembled in Figure 9. It prints netpag ⁇ s on Letter/A4 sized media using duplexed 8Va" MemjetTM print engines 602 and 603, as shown in Figures 10 and 1Oe. It uses a straight paper path with the paper 604 passing through the duplexed print engines 602 and 603 which print both sides of a sheet simultaneously, in full color and with full bleed.
  • An integral binding assembly 605 applies a st ⁇ p of glue along one edge of each printed sheet, allowing it to adhere to the previous sheet when pressed against it. This creates a final bound document 618 which can range in thickness from one sheet to several hundred sheets.
  • the replaceable ink cartridge 627 shown in Figure 12 coupled with the duplexed print engines, has bladders or chambers for storing fixative, adhesive, and cyan, magenta, yellow, black and infrared inks.
  • the cartridge al9o contains a micro air filter in a base molding.
  • the micro air filter interfaces with an air pump 638 inside the printer via a hose 639. This provides filtered air to the prlntheads to prevent ingrcis of micro particles into tbe MemjetTM printheads 350 which might otherwise clog ⁇ V printhead nozzles.
  • the air filter witbm the cartridge, the operational life of the filter is effectively linked to the life of tbe cartridge.
  • the ink cartridge is a fully recyclable product with a capacity for printing and gluing 3000 pages (1500 sheets).
  • the motorized media pick-up roller assembly 626 pushes the top sheet directly from the media tray past a paper sensor on the first print engine 602 into the duplexed MemjetTM prLnthead assembly.
  • the two MemjetTM print engines 602 and 603 are mounted in on opposing in-line sequential configuration along me straight paper path
  • the paper 604 is drawn into the first print engine 602 by integral, powered pick-up rollers 626.
  • the position and size of the paper 604 is sensed and ftill bleed printing commences. Fixative is printed simultaneously to aid drying in the shortest possible tinv
  • the paper 604 peases from the duplexed print engines 602 and 603 into the binder assembly 605.
  • the printed page passes berween a powered spike wheel axle 670 with a fibrous ⁇ upport roller and another movable axle with spike wheels and a momentary action glue wheel.
  • Too movable axle/glue assembly 673 is mounted to a metal support bracket and it ⁇ transported forward lo interface with the powered axle 670 via gears by action of a camshaft.
  • a separate motor powers this camshaft.
  • the glue wheel assembly 673 consists of a partially hotlow axle 679 with a rotating coupling for the glue supply hose 641 from the ink cartridge 627.
  • This axle 679 connects to a glue wheel, which absorbs adhesive by capillary action through radial holes.
  • a molded housing 692 surrounds the glue wheel, with an opening at the from. Pivoting side moldings and sprung outer doors are attached to the metal bracket and hinge out sideways when the rest of the assembly 673 is thrust forward. This action exposes the glue wheel through the front of the molded housing 682. Tension springs close toe assembly and effectively cap the glue wheel during periods of inactivity. As the sheet 604 passes into the glue wheel assembly 673, adhesive is applied to one vertical edge on the front side (apart from the first sheet of a document) as it is transported down into the binding assembly 605.
  • PRODUCT TAGGING Automatic identification refers to the use of technologies such as bar codes, magnetic stripe cards, smartcards, and RF transponders, to (s ⁇ -cu-)autor ⁇ atically identify objects to data processing systems without manual keying.
  • a product item is commonly identified by a 12 -digit
  • UPC Universal Product Code
  • the most common UPC numbering system incorporates a 5-digit manufacturer number and a 5-digic item number.
  • UPC is used to identify a class of product rather than a ⁇ individual product item.
  • the Uniform Code Council and EAN International define and administer the UPC and related codes as subsets of the 14-digit Global Trade Item Number (GTIN).
  • RFID tags in the form of so-called two-dimensional bar codes
  • RFID tags radio frequency identification
  • Optical tags have me advantage of being inexpensive, but require optical line-of-sjght &r reading.
  • RFID tags have the advantage of supporting onmidirection-tl reading, but are comparatively expensive. The presence of metal or liquid can seriously interfere with RFID tag performance, undermining the omnidirectional reading advantage.
  • the Massachusetts Institute of Technology (MlT) A ⁇ o-ID Center has developed a standard for a 96-bit Electronic Product Code (EPC), coupled with an Internet-based Object Name Service (ONS) and a Product Markup Language (PML).
  • EPC Electronic Product Code
  • ODS Internet-based Object Name Service
  • PML Product Markup Language
  • EPC consists of an 8-bit header, a 28-bit EPC manager, a 24-bit object class, and a 36-bit serial number.
  • EPC Electronic Product Code
  • M]T Auto-ID Center January 2001
  • the Auto-ID Center has defined a mapping of the GTIK onto the EPC to demonstrate compatibility berween the EPC and current practices Brock, D L , Integrating the Electronic Product Code (EPC) and the Global Trade Item Number (GTIN), MIT Auto-ID Center (November 2001), the contents of which are herein incorporated by cross-reference.
  • the EPC is administered by EPCglobal, an EAN-UCC joint venture.
  • EPCs are technology-neutral and oan be encoded and carried in many forms.
  • the Auto-ID Center strongly advocates the use of low-cost passive RFID tags to carry EPCs, and lias defined a 64-bit version of the EPC to allow the cost of RFID tags to be minimized ut the aho ⁇ term.
  • low- cost RFID teg characteristic* refer to Sarma, S., Towards the Sc Tag, M ⁇ T Auto-ID Center (November 2001), the contents of which are herein incorporated by cross-reference.
  • a description of a commerciatiy- available low-cost passive RFID tag refer to 915 MHz RFID Tag, Alien Technology (2002), the contents of which are herein incorporated by cross-reference.
  • the 64-bit EPC refer to Brock, D.L., The Compact Electronic Product Code, MTT Auto-ID Center (November 2001), the contents of which are herein incorporated by cross-reference.
  • EPCs are intended not just for unique item-level tagging and tracking, but also for case-level and pallet-level tagging, and for tagging of other logistic units of shipping and transportation such as containers and trucks.
  • the distributed PML database records dynamic relationships between items and h j gocr-levd containers In the packaging, shipping and transportation hierarchy.
  • an invisible (e.g. infrared) tagging scheme to uniquely identify a product item has the significant advantage that it allows the entire surface of a product to be tagged, or a significant portion thereof; without impinging on the graphic design of the product's packaging or labelling. If the entire product surface is tagged, then the orientation of the product doesn't affect its ability to be scanned, i.e. a significant part of the line-of-sight disadvantage of a visible bar code is eliminated. Furthermore, since the tags are small and massively replicated, label damage no longer prevents scanning. O ⁇ raitegging, then, consists of covering a large proportion of the surface of a product item with optically-readable invisible tags.
  • Each onmitag uniquely identifies the product item on which it appears.
  • the omaitag may directly encode the product code (e.g. EPC) of the item, or may encode a surrogate IO which in turn identifies the product code via a database lookup.
  • Each ornnitag also optionally identifies its own position on the surface of the product item, to provide the downstream consumer benefits of netpage interactivity described earlier.
  • Omniugs are applied during product manufacture and/or packaging using digital printers. These may be add-on infrared printers which print the omrutags after the text and graphics have been printed by other means, or integrated color and infrared printers which print the omnitags, text and graphics simultaneously. Digitally-printed text and graphics may include everything on the label or packaging, or may consist only of the variable portions, with other portions still printed by other means. 4.2 OMNITAGGING
  • a product's unique item ID 2 I S may be seen as a special kind of unique object ID 210.
  • the Electronic Product Code (EPC) 220 is one emerging standard for an item DD.
  • An item ID typically consists of a product ID 214 and a serial number 213.
  • the product QD identifies a class of product, while tbe serial number identifies a particular instance of that class, i.e. an individual product item.
  • the product ID in turn typically consists of a manufacturer number 2) 1 and a product class number 212.
  • the best-known product ID is the EAKUCC Universal Product Code (UPC) 221 and its variants.
  • UPC EAKUCC Universal Product Code
  • an omnitag 202 encodes a page ID (or region ID) SO and a two- dimensional (2D) position 66.
  • the region ID identifies me surface region containing the tag, and the position identifies tbe tag's position within the two-dimensional region. Since the surface in question is the surface of a physical product item 201, it i ⁇ useful to define a one-to-one mapping between the region ID and the unique object ID 210, and more specifically the item ID 215, of the product item. Note, however, that the mapping can be many-to-one without compromising the utility of me omnitag. For example, each panel of a product item's packaging could have a different region ID S0. Conversely, the omniug may directly encode the item
  • region ID contains the item ID, suitably prefixed to decouple item ID allocation from general netpage region ID allocation. Note that the region ID uniquely distinguishes the corresponding surface region from all other surface regions identified within tbe global netpage system.
  • the item DD 215 is preferably the EPC 220 proposed by the Auto-ID Center, since this provides direct compatibility between omnitags and EPC-carrying RFID tags.
  • the position 66 is shown as optional. This id to indicate that much of the utility of tbe omrutag in the supply chain derives from the region ED 50, and the position may be omitted if not desired for a particular product.
  • an omnitag 202 is a netpage tag 4, i e. it has me logical structure, physical layout and semantics of a netpage tag.
  • a netpage sensing device such as the netpage pen 101 images and decodes an omnitag, it uses the posi ⁇ oo and orientation of the tag in its field of view end combines this with the position encoded in the tag to compute its own position relative to the lag. As tbe sensing device is moved relative to a
  • Hyperlabelled surface region it is thereby able to track its own motion relative to tb ⁇ region and generate a set of timestamped position samples representative of its time-varying path.
  • the sensing device is a pen
  • the path consists of a sequence of strokes, with each stroke starting when the pen makes contact with the surface, and ending when the pen breaks contact with the surface.
  • the server retrieves a description of the region keyed by region ID, and interprets the stroke in relation to the description. For example, if tbe description includes a hyperlink and the stroke intersects the zone of the hyperlink, then the server may interpret the stroke as a designation of tbe hyperlink and activate the hyperlink
  • An omnitag primer is a digital printer which prints ommtag- onto the label, packaging or actual surface of a product before, during or after product manufacture and/or assembly. It is a special case of a nerpage printer 601. It is capable of printing a continuous pattern of omnitags onto a surface, typically using a near-iofrared-abso ⁇ tive ink. In high-speed environments, the printer includes hardware which accelerates tag rendering. This typically includes real-tune Reed-Solomo ⁇ encoding of variable tag data such as tag position, and real-time template-based rendering of the actual tag pattern at the dot resolution of tbe pnntbead.
  • the printer may be an add-on infrared printer which prints the omnitags after text and graphics have been printed by other means, or an integrated color and infrared printer which prints the omnitags, text and graphics simultaneously Digitally-printed text and graphics may include everything on the label or packaging, or may consist only of tbe variable portions, with other portions still printed by other means.
  • an omnitag printer with an infrared and black printing capability can displace an existing digital printer used for variable data printing, such as a conventional thermal transfer or inkjet printer.
  • any reference to printing onto an item label is intended to include printing onto (he item packaging in general, or directly onto the item surface.
  • any reference to an item BD 215 i6 intended to include a region ID S0 (or collection of per-panel ' region ids), or a component thereof.
  • the printer is typically controlled by a host computer, which supplies the printer with fixed and/or variable text and graphics as well as item ids for inclusion in the omnitags.
  • the host may provide real-time control over the printer, whereby it provides the printer with data in real time as printing proceeds. As an optimisation, the host may provide the printer with fixed data before printing begins, and only provide variable data in real ctcuc.
  • Tbe printer may also be capable of generating per-itera variable data based on parameters provided by the host For example, the host tnay provide the printer with a base item ID prior to printing, and the printer may simply increment tho base item UD to generate successive item ids.
  • memory in tbe ink cartridge or other storage medium inserted into the printer may provide a source of unique item ids, in which case the printer reports the assignment of items ids to tbe host computer for recording by the host.
  • the printer may be capable of reading a pre-existing item ID from the label onto which tbe omnitags are being printed, a ⁇ suming tbe unique ID has been applied in some form to tbe label during a previous manufacturing step.
  • the item ID may already be present i ⁇ the form of a visible 2D bar code, or encoded in an RFID tag.
  • the printer can include an optical bar code scanner.
  • it can include an RFtO reader.
  • the printer may also be capable of rendering the item ID in other forms. For example, it may be capable of printing the item ID in the form of a 2D bar code, or of printing the product ED component of the item ID in the form of a ID bar code, or of writing the item ID to a writable or write-once RFID tag.
  • Both fixed and hand-held scanners may be used to scan omnitagged product items, using both laser-based 2D scanning and 2D image-sensor-based scanning, using similar or the same techniques 89 employed in the netpage pen.
  • both a fixed scanner 254 and a hand-held scanner 252 communicate scan data to the product server 251.
  • the product server may in mm communicate product item event data to a peer product server (not shown), or to a product application server 2S0, which may implement sharing of data with related product servers. For example, stock movements within a retail store may be recorded locally on the retail store's product server, but the manufacturer's product server may be notified once a product item Ls sold.
  • a product item whose labelling, packaging or actual surface has boon omnitaggcd provides the same level of interactivity as any other netpage.
  • Netpage-compatible product tagging There is a strong case to be made for netpage-compatible product tagging.
  • Netpage rums any printed surface into a finely differentiated graphical user interface akin to a Web page, and there are many applications which map nicely onto the surface of a product. These applications include obtaining product information of various kinds (nutritional information; cooking instructions; recipes; related products; u ⁇ -by dates; servicing instructions; recall notices); playing games; entering competitions; managing ownership (registration; query, such as in the case of stolen goods; transfer); providing product feedback; messaging; and Indirect device control.
  • product information of various kinds (nutritional information; cooking instructions; recipes; related products; u ⁇ -by dates; servicing instructions; recall notices); playing games; entering competitions; managing ownership (registration; query, such as in the case of stolen goods; transfer); providing product feedback; messaging; and Indirect device control.
  • the burden of information navigation is transferred to the information delivery device, which may significantly increase me complexity of the user experience or the required sophistication of the delivery device user interface.
  • the thick slurry was distilled for 2 h to remove the methanol and toluene. Once the toluene had distilled off, the reaction mixture became homogeneous and less viscous and stirred readily. Heating was continued for 3 h at 190 °C (internal). The brown/black reaction mixture was cooled to 60 °C, diluted with chloroform (I S0 mL), and filtered under gravity through a sintered glass runnel The solid residue was washed with more chloroform (50 mL) and then a further portion (50 mL) with suction under reduced preasure.
  • Napbtnalocyaninatogaltium methoxytriethyleneoxide 3 (9.38 g; 0.010 mol) was treated with 30% oleum (47 mL) by slow addition via a dropping runnel while cooling in an ice/water bath under a nitrogen atmosphere. Upon completion of the addition, the reaction mixture was transferred to a preheated water bath at 55 °C and stirred at this temperature for 2 b during which time the mixture became a homogeneous viscous dark blue solution. The stirred reaction mixture was cooled in an ice/water bath and then 2-propanol (40 mL) was added slowly via a dropping funnel.
  • the -olid was filtered off and washed with ether/emanol (50:50, 2 x 5 tnL) and ether (2 x 5 mL). After drying under high vacuum, the tetrapyridituura salt ⁇ was obtained as a green powder (136 mg; 56%).
  • Hydroxygallium naphthalocyaninetetrasulfonic acid 4 (1.40 g; 1.25 mmol) end imidazole (0596 g; 8.75 mmol) we T ⁇ suspended in memanol/water (80:20; 17.5 mL) and then the resulting green mixture was sttrred at room temperature for 2 h, becoming homogeneous after 1 b.
  • the solution was diluted with diethyl ether (50 mL), stirred for 15 coin, and theo allowed to stand. The supernatant liquid was decanted off and then ether/methanol (50:50; 20 mL) was added with stirring.
  • Example 3 Preparation of Inks and Reflecfaf ⁇ ff fipeftra of Ammonium Salts A solution of each salt was made up in an ink vehicle according to Table 1.
  • Example 3(i) uses tnbutylamine in a ratio of 1 : 1 and provides a formulation having a Q-band at 605 am.
  • tributylamine in a ratio of 4: 1 (Table 2) provides a formulation having a blue-shifted Q-band at 792 nm.
  • Inks according to tbe present inveotioo may also be prepared without isolation of the naphthalocyanine salt-.
  • the tetrasulfbt ⁇ c acid 4 may be formulated in an ink vehicle and the pH adjusted using a suitable base or buffer. Examples 4(a) and 4 ⁇ ) below describe me preparation of inks by addition of carboxylase salts in an ink comprising the tetraulforuc 4.
  • the tetrasulfonic acid 4 was made up to 2 mM in ink vehicle B containing 8 mM NaOAc or UOAc. This gave a clear green solution containing 6 (pH 5.1) that was printed otv Celcast matt pbotoquality inkjet paper ( 143 £sm). The reflectance spectrum bad X 0-U 806 nm for both sodium and lithium.
  • the tetrasulfonic acid 4 was made up to 1.5 mM in ink vehicle B containing 3 mM ethylenediaminetetraaceric acid (EDTA) disodium salt. This gave a clear green solution (pH 3.7) that was printed on Celcast matt pbotoquality InkJet paper (143 gam). The reflectance spectrum bad X n ⁇ 805 nm.
  • EDTA ethylenediaminetetraaceric acid
  • Example 5 Preparation and Reflectance Spectra of Inks Comprising Mixed Salts
  • Inks according to the present invention may also comprise mixed salts.
  • Mixed salts may be advantageous m providing a suitable balance of properties or for tuning the spectroscopic characteristics of a salt.
  • the direct addition of three equivalents of p-toluenesulfo ⁇ ic acid to the tetrak j s(DBUammoniura) salt 9 in the ink formulation lowers the pH from 7.7 to 4.0 and shifts the Q-band to 806 am indicating that protonatio ⁇ of the interna) mero-nitrogens ha* taken place.
  • the DBUammonium salt 9 (26.3 rag; 15.2 ⁇ mol) and p-toluene ⁇ ulfonk acid (8.63 mg; 45.6 ⁇ mol) were dissolved in ink vehicle B (11.2 mL) to make up a solution that was 1 36 mM with respect to the napbthalocyanine. This gave a clear green solution (pH 4.0) that was printed on Celcast matt photoquality inkjei paper (143 gsm). The reflectance spectrum had ⁇ r ⁇ » 806 run ( Figure 30).
  • the tetraimidazolium salt 7 was made up to 1 5 mM in ink vehicle B containing 3 mM acetic acid. This gave a clear green solution (pH S l) that was printed on Celcasi mart photoquality inkjet paper (143 gsm). The reflectance spectrum bad K ⁇ , 807 nra ( Figure 31 ).
  • An O ⁇ ratn 250 W metal halide lamp (HQI-EP 250W/D E40) with an intensity of 17,000 lumens, (approximately 70,000 lux) was used to irradiate printed samples positioned at a distance of 9.0 cm from the globe.
  • the industry standard measurement of lightfastness is the tune taken for a sample to fade by 30% under typical indoor lighting conditions. Typical indoor lighting conditions are defined as illumination under a lighting intensity of 500 lux for 10 hours per day.
  • LiEhtfestness - Time taken to fade by 30% x (70,000 lux / 500 lux) x (24 h / 10 b) Time taken to fedc by 30% * 336
  • Example 7 - Ozonefastness Inks were formulated from a variety of salts using the ink vehicles A, B, C 1 D, F, H or I.
  • Ink vehicles AO were described in Table I above.
  • Table 6 below describes ink vehicles D, F, H and I.
  • Inks according to the present invention were ⁇ hown to have acceptable ozonefeseness, in addition to acceptable ligbtrast ⁇ ess.
  • gallium napnthalocyanine salts and ink fbnnulaiioos of the present invention are excellent for use with ⁇ etpage and HyperlabelTM systems.
  • These dyes and inks exhibit near-IR absorpcion above 800 tun, good solubility id inkjet ink formulations, negligible or low visibility and excellent light&itocii.
  • these dyes can be prepared in a rugh>y>elding, expedient and efficient synthesis.

Abstract

There is provided an aqueous formulation comprising an IR-absorbing naphthalocyanine dye of formula (II): or a salt form thereof, wherein: M is Ga(A1); A1 is an axial ligand selected from -OH, halogen, -OR3, -OC(O)R4 or -O(CH2CH2O)eR6 wherein e is an integer from 2 to 10 and R6 is H, C1-8 alkyl or C(O)C1-8 alkyl; R1 and R2 may be the same or different and are selected from hydrogen or C1-2 alkoxy; R3 is selected from C1-2 alkyl, C5-I2 aryl, C5-12 arylalkyl or Si(Rx)(Ry)(Rz); R4 is selected from C1-12 alkyl, C5-12 aryl or C5-12 arylalkyl; and Rx, Ry and Rz may be the same or different and are selected from C1-12 alkyl, C5-12 aryl, C5-12 arylalkyl, C1-12 alkoxy, C1-12 aryloxy or C5-12 arylalkoxy. The formulation has a pH in the range of 3,5 to 7 and is particularly suitable for use as an IR- absorbing inkjet ink, providing compatibility with known CMYK, inks together with an optimally red-shifted λmax

Description

IMPROVEMENTS IN INK FORMULATIONS COMPRISING GALLIUM NAPHTHALOCYANINES
Field of the Invention
The present application relates to infrared (IR) dyes, in particular near-IR dyes, which are synthetically accessible in high yield and which are ΛspersibJc in an aqueous ink base. It has been developed primarily for providing Bt inks compatible with CMYK inks, and for optimizing IR-absorption
Background of the Invention
IR absorbing dyes have numerous applications, such as optical recording systems, thermal writing displays, laser fitters, infrared photography, medical applications and printing. Typically, it is desirable for the dyes used in these applications to have strong absorption in the near-IR at the emission wavelengths of semiconductor lasers (e.g. between about 700 and 2000 nra, preferably between about 700 and 1000 nm). In optical recording technology, for example, gallium aluminium arsenide (GaAlAs) and indium phosphide (InP) diode lasers are widely used as light sources.
Another important application of IR dyes is in inks, such as printing inks. The storage and retrieval of digital information in printed form is particularly important. A familiar example of this technology is the use of primed, scannable bar codes. Bar codes are typically printed onto tags or labels associated with a particular product and contain information about the product, such aβ its identity, price etc. Bar codes are usually printed in lines of visible black ink, and detected using visible light from a scanner. The scanner typically comprises an LED or laser (e.g. a HeNe User, which emits light at 633 nm) light source and a photocell for detecting reflected light. Black dyes suitable for use in barcode inks are described w, for example, WO03/074613. However, in other applications of this technology (e.g. security tagging) it is desirable to have a barcode, or other intelligible marking, printed with an ink that is invisible to the unaided eye, but wtuch can be detected under UV or IR light
An especially important application of detectable invisible ink is in automatic identification systems, and especially "neipage" and "Hyperlabel™" systems. Netpage systems are the subject of a number of patents and patent applications some of which are listed in the cross-reference section above and , all of which are incorporated herein by reference.
In general, the netpage system relies on the production of, and human interaction with, nerpages.
These are pages of text, graphics and images printed on ordinary paper, but which work like interactive web pages. Information is encoded on each page using ink which is substantially invisible to the unaided human eye. The ink, however, and thereby the coded data, can be sensed by an optically imaging pea and transmitted to the netpage system.
Active buttons and hyperlinks oo each page may be clicked with the pen to request information from the network or to signal preferences to a network server. In some forms, text written by band on a netpage may be automatically recognized and converted to computer text in the netpage system, allowing forms to be filled in. In other forms, signatures recorded on a nelpage may be automatically verified, allowing e-commerce transactions to be securely authorized.
Netpages are the foundation on which a netpage network is built They may provide a paper-based user interface to published information and interactive service..
A netpage consists of a printed page (or other surface region) invisibly tagged with references to an online description of the page. The online page description is maintained persistently by a oetpage page server. The page description describes the visible layout and content of the page, including text, graphics and images. It also describes the input elements on the page, including buttons, hyperlinks, and input fields. A oetpage allows markings made with a netpage pen on its surface to be simultaneously captured and processed by the netpage system. Multiple netpages can share the same page description. However, to allow input through otherwise identical pages to be distinguished, each oβtpage is assigned a unique page identifier. This page ID has sufficient precision to distinguish between a very large number of nβtpages.
Each reference to the page description is encoded in a printed tag. The tag identifies the unique page on which it appears, and thereby indirectly identifies the page description. The tag also identifies its own position on the page.
Tags are printed in infrared-absorptive ink on any substrate which is infrared-reflective, such as ordinary paper. Near-infrared wavelengths are invisible to the human eye but are easily sensed by a solid- state image sensor with an appropriate fitter.
A tag is sensed by an area image sensor in the netpage pen, and the tag data is transmitted to die netpage system via the nearest netpage printer. The pen is wireless and communicates with the netpage printer via a short-range radio link- Tags are sufficiently small and densely arranged (hat the pen can reliably image at least one tag even on a single click on the page. It is important that the pen recognize the page ID and position on every interaction with the page, since the interaction is stateless. Tags are error-correctably encoded to make them partially tolerant to surface damage. The netpage page server maintains a unique page instance for each printed netpage, allowing it to maintain a distinct set of usor-sυppued values for input fields in the page description for each printed netpage.
Hyperlabel™ is a trade mark of Silverbrook Research Pty Ltd, Australia. In general, Hyperlabel™ systems use an invisible (e.g. infrared) tagging scheme to uniquely identity a product item. This has the significant advantage that it allows the entire surface of a product to be tagged, or a significant portion thereot without impinging on tho graphic design of the product's packaging or labeling. If the entire surface of a product is tagged ("omnitagged"), then the orientation of the product does not affect its ability to be scanned i.e. a significant part of the line-of-sight disadvantage of visible barcodes is eliminated. Furthermore, if the tags are compact and massively replicated ("omiutags"), then label damage no longer prevents scanning.
Thus, hyperlabelling consists of covering a large portion of the surface of a product with optically- readable invisible tags. When the tags utilize reflection or absorption in the infrared spectrum, they are referred to as infrared identification (IRID) tags. Each Hyperlabel™ tag uniquely identifies the product on which it appears. The tag may directly encode the product code of the item, or it may encode a surrogate ID which in turn identifies the product code via a database lookup. Each tag also optionally identifies its own position on the surface of the product item, to provide the downstream consumer benefits of netpage interactivity.
Hypcrlabels™ are applied during product manufacture and/or packaging using digital printers, preferably inkjet printers. These may be add-on infrared primers, which print the tags after the text and graphics have been printed by other means, or integrated colour and infrared printers which print the tags, text and graphics simultaneously.
Hyperlabels can be detected using similar technology to barcodes, except using a light source having an appropriate near-IR frequency. The light source may be a laser (e.g. a GaAlAs laser, which emits light at 830 run) or it may bo an LED.
From the foregoing, it will be readily apparent that invisible IR detectable inks are an important component of netpage and Hyperlabel™ systems. In order for an IR abβorbing ink to function satisfactorily in these systems, it should ideally meet a number of criteria:
(i) compatibility of the IR dye wim traditional inkjet inks; (ii) compatibility of the IR dye with aaiieous solvents used ώ inkjet inks; (lii) iflterωe absorption in the near infra-red region (e g. 700 to 1000 nm); (iv) zero or low intensity visible absorption;
(v) lightmstnesa; (vi) thermal stability; (vti) zero or low toxicity; (viu) low-cost manufacture; (ix) adheres well to paper and other media; and
(x) no strikethrougb and f'"*rrm' bleeding of the ink on printing.
Hence, it would be desirable to develop IR dyes and ink compositions fulfilling at least some and preferably all of the above criteria. Such inks are desirable to complement nβtpage and Hyperlabel ™ systems. Some [R dyes are commercially available from various sources, such as Epolin Products, Avecia
Inks and H W. Sands Corp.
In addition, the prior an describes various IR dyes. US 5,460,646, for example, describes an infrared printing ink comprising a colorant, a vehicle and a solvent, wherein the colorant is a silicon (TV) 2,3- nβpbthalocyanine bis-trialkylsilyloxide. US 5,282,894 describes a solvent-based printing ink comprising a metal-free phthalocyanine, a coraplexed phtbalocyanine, a metαl-frec rupbttωlocyanine, a complexed napbtbalocyβnine, a nickel dithiolene, an aminium compound, a raeihiiie compound or on azulenesqtiaric acid.
However, none of these prior art dyes can be formulated into ink compositions suitable for use in netpage or Hyperlabel™ systems. In parricuiar, commercially available end/or prior art inks sutler from one or more of the following problems: absorption at wavelengths unsuitable for detection by ocar-IR sensors; poor solubility or dispersibility in aqueous solvent systems; or unacceptably high absorption in the visible part of Ae spectrum.
In our earlier US patent application no. 10/986,402 (the contents of which is herein incorporated by reference), we described a water-soluble gallium naphthalocyanine dye fulfilling many of the desirable properties identified above. The dye typically comprises four sulfonic acid groups, which impart a high degree of water-solubility, either in trε acid or salt form. However, it has since been found that rhe formation of saJts using, for example, sodium hydroxide or tnethylamine produces an unexpected blue-shift in the Q- band (X11B1) of the dye, from about 80S DID to about 790 tun or less On the one hand, salt formation is desirable because it raises the pH of the dye in solution mat-ing it compatible with other CMYK inks. Typically, CMYK inks have a pH in the range of 8-9, so a strongly acidic IR ink would potentially cause precipitation of ink components if the IR and CMYK inks are mixed on a pnnthead face during purging. On the other hand, blue-shifting of the Q-band caused by 9alτ formation makes these dyes less appealing as IR ink candidates, because they must be used in higher concentrations to have acceptable detectabilicy by an IR sensor, resulting in the ink appearing more colored.
These contradictory requirements of the IR dye need to be addressed in order to formulate an FR ink having optimal performance in netpage and Hyperlabel™ applications.
Summary of the Invention
In a first aspect, there iβ provided an IR-absorbing napbthalocyanine dye of formula (I):
Figure imgf000006_0001
wherein:
M is Ga(A1);
A1 is an axial ligand selected from -OH, halogen, -OR1, -OC(O)R4 or -O(CH2CH2O)CR" wherein e iβ an integer from 2 to IO and R' is H, C,.5 alkyl or C(O)C,.β βlkyl.;
R1 and R: may be the same or different and are selected from hydrogen or CM2 alkoxy; R3 is selected from C11 alkyl. C5.,j aryt, C5.l2 arylalkyl or Si(RW)(RO;
R4 iβ selected from C|.1j alkyl. C3.n aryi or Cj.u arylalkyl;
R", Ry and R* may be the same or different and are selected from C1. ,2 alkyL C3-I2 aryl, C5.12 arylalkyl, C,.,j alkoxy, C$.,j aryloxy or Cj-u arylalkoxy, and each B is independently selected from a base, wherein BH" has a pK, of between 4 and 9
Alternatively, there is provided an aqueous formulation comprising an JR-absorbing napbtbalocyaoine dye of formula (Tl):
Figure imgf000007_0001
or a salt form thereof, wherein:
M is Ga(A1);
A' is an axial Ugand selected from -OH, halogen, -OR1, -OC(O)R4 or -O(CH2CH2O)JR* wherein e is an integer from 2 to 10 and Rc is H, C,.β alkyl or C(O)C14 alkyl;
R1 and R2 may be the same or different and are εelected from hydrogen or C|.1j alkoxy; RJ is selected from C1.,; alky], Cy11 aryl, C,.,: arylalkyl or Si(R*)(RO(Rr);
R* iβ selected from C|.u alky), C$.u aryl or C5.u arylalkyk and
R1, Ky and R1 may be the same or different and are selected from C|.u aflcyl, C$.|2 ary), C^n arylalky I, CM2 alkoxy, C5.12 aryloxy or C$.u arylalkoxy; said formulation having a pH in the range of 3.5 to 7. In a second aspect, there is provided an inkjet ink comprising a dye or a formulation as described above.
In a third aspect, there is provided an inkjet printer comprising a printhead in fluid communication with at least one ink reservoir, wherein said at least one ink reservoir comprises an inkjet ink as described above. In a fourth aspect, there is provided an ink cartridge for an inkjet printer, wherein said ink cartridge comprises an inkjet ink as described above.
IQ a fifth aspect, there is provided β βubβtrate having a dye as described above disposed thereon. In a sixth aspect, ihβrβ is provided a method of enabling entry of data into a computer syetem via a primed form, the form containing human-readable information and machine-readable coded data, the coded data being indicative of an identity of the form and of a plurality of locations on the form, the method including the steps of: receiving, in the computer system and from a sensing device, indicating data regarding the identity of the form and a position of the sensing device relative to the form, the sensing device, when placed in an operative position relative to the form, generating the indicating data using at least some of the coded data; identifying, in Ae computer system and from the indicating data, at least one field of the form; and interpreting, in the computer system, at least some of the indicating data as it relates to the at least one field, wherein said coded data comprises an IR-absorbing dye as described above.
In a seventh aspect, there is provided a method of interacting with a product item, the product item having a printed surface containing human-readable Information and machine-readable coded data, the coded data being indicative of an identity of the product item, the method including the steps of: (a) receiving, in the computer system and from a sensing device, indicating data regarding the identity of the product item, the sensing device, when placed in an operative position relative to the product item, generating the indicating data using at least some of the coded data; and
(b) identifying, in the computer system and u-ύng the indicating data, an interaction relating to the product item, wherein said coded data comprises an IR-absorbing dye according as described above.
Brief Description of Drawings
Figure 1 is a schematic of a the relationship betweeo a sample printed netpage and its online page description; Figure 2 is a schematic view of a interaction between a netpage pen, a Web terminal, a netpage printer, a netpage relay, a netpage page server, and a netpage application εerver, and a Web server,
Figure 3 illustrates a collection of netpage servers, Web terminals, printers and relays interconnected via a network;
Figure 4 is a schematic view of a high-level structure of a printed netpage and its online page description;
Figure 5a is a plan view showing the inKrrUsaving and rotation of the symbols of four codewords of the tag;
Figure Sb is a plan view showing a roacrodoi layout for the tag shown in Figure 5a;
Figure 5c is a plan view showing an arrangement of nine of the tags shown Ln Figures Sa and Sb, in which targets are shared between adjacent tags;
Figure Sd is a plan view showing a relationship becween a set of the tags shown in Figure 5a and a field of view of a netpage sensing device in the form of a netpage pen;
Figure 6 is a perspective view of a netpage pen and its associated tag-sensing field-of-view cone;
Figure 7 is a perspective exploded view of the netpage pen shown in Figure 6; Figure 8 is β schematic block diagram of a pen controller for the netpage pen shown in Figureβ 6 and 7; Figure 9 is a perspective view of a wall-mounted netpage printer.
Figure 10 is a section through the length of the netpage printer of Figure 9;
Figure 10a ia ao enlarged portion of Figure 10 showing a section of the duplexed print eαgines and glue wheel assembly, Figure H is a detailed view of the ink cartridge, ink, air and glue paths, and print engineβ of the netpage printer of Figures 9 and 10;
Figure 12 is an exploded view of an ink cartridge;
Figure 13 is a schematic view of the structure of an item ID;
Figure 14 is a schematic view of the structure of an omnitag; Figure 15 is a schematic view of a pen class diagram;
Figure 16 is a schematic view of the interaction between a product item, a fixed product 9oannβr, a hand-held product scanner, a scanner relay, a product server, and a product application server;
Figure 17 is a perspective view of a bi-lithic printhead;
Figure 18 an exploded perspective view of the bi-lithic princhead of Figure 17; Figure 19 is a sectional view through one eod of the bi-lithic printbiad of Figure 17;
Figure 20 is a longitudinal sectional view through the bι-litbic printhead of Figure 17;
Figures 21 (a) to 2l(d) show a side elevation, plan view, opposite side elevation and reverse plan view, respectively, of the bi-lithic printhead of Figure 17;
Figures 22 (a) to 22(c) show this basic operational principles of a ttusrroal bend actuator; Figure 23 shows a three dimensional view of a single ink jet nozzle arrangement constructed in accordance with Figure 22;
Figure 24 shows an array of the nozzle arrangements shown in Figure 23;
Figure 25 is a schematic croββ-sectional view through an ink chamber of a unit cell of a bubble forming heater element actuator. Figure 26 shows a reflectance spectrum of hydroxy ealuwn napbtbalocyBninetetπυulfonic acid 4;
Figure 27 shows a 1H NMR spectrum of hydroxygallium naphthalocyaninetetrasulfonic acid 4 in 4rDMSO (0.1% w/v);
Figure 28 βhowa a reflectance spectrum of tetraiαύdazouum bydroxygallium oaphthatocyaninetetrasulfonale 7; Figure 29 shows a reflectance spectrum of tetrakisφBUamnionium) hydroxygallium naphthalocyaninetetrasulfonate 9;
Figure 30 shows a reflectance spectrum of tetrakis(DBUaaunonium) hydroxygaJlium napbthalocyaninetetrasulfonate 9 wiihp-toluenesulfonic acid (3 equivalents);
Figure 31 shows a reflectance spectrum of tetraimidazolium hydroxygallium naphthalocvantnetetrasulfonate 7 with two equivalents of acetic acid.
Detailed Description Jfi-^bxorhiηg Etye
As used herein, the term "IR-absorbing dye" means a dye substance, which absorbs infrared radiation and which is therefore suitable for detection by so infrared sensor. Preferably, the IR-absorbing dye absorbs in the near infrared region, and preferably has a X0n* in the range of 700 to 1000 ran, more preferably 750 to 900 nm, more preferably 780 to 850 nm. Dyes having a λ^ in chis range are particularly suitable for detection by semiconductor lasers, such as a gallium aluminium arsenide diode User.
As will be explained in more detail below, dyes represented by formula (I) may be to equilibrium with other tautoraers in which me∞-nitrogenfs) of the naphthalocyanine ring system are protonated. Indeed, the dye represented by formula (T) may only be β minor species in ttus equilibrium. However, by convention, dyeβ according to the present invention are generally represented by formula Q). Other tautomere in equilibrium therewith are, of course, included within the scope of the present invention.
Dyes according to the present invention have the advantageous features of: optimal absorption in the near-IR region; suitability for formulation into aqueous inkjet inks; pH compatible with known CMYK inka without sacrificing optimal near-IR absorption; and facile preparation. Moreover, their high extinction coefficients in the near-IR region means that the dyes appear "invisible" at a concentration suitable for detection by a near-IR detector (e.g. a netpage pen). Accordingly, the dyes of the present invention are especially suitable for use in ncrpage and Hyperlabel™ applications. None of the dyes known in the prior art has this unique combination of properties. Tbo present invention was initially conceived by observing the reaction of a gallium naphthalocyanine tetiasulfooic acid salt with four equivalents of amine to given an ammonium salt. It was found, surprisingly, that the reflectance 9pectra of ammonium (alts are independent of the structure of the amine, but very much affected by the pK, of the ammonium salt. At low pK« the Q-band (X^J baa a large monomeric component and is red-shifted to 800-810 ran. However, when strongly basic amines are used, die Q-band exhibits a significant dimer or aggregate component and the monomer component is blue shifted to <800 nm. Given that the internal meso nitrogens of the napbtnalocyanine ring system have pK, values of about 11.5 (first protonation) and 6.7 (second protonation), then without wishing to bo bound by theory, these results have been interpreted in terms of toe ability of the ammonium ion to protonate zero (structure A), one (structure B) or two (structure C) of the meso nitrogens. The greater the prorønaiing ability of the ammonium ion (lower pKa), the greater the degree of protonation of the macrocyck. It is believed that protonation of the macrocycle reduces π-π stacking between adjacent molecules by electrostatic repulsion. With less aggregation and a greater monomer component, a red-shift of the Q-band of the salt is observed.
Figure imgf000010_0001
Following on from these surprising results, it was then (bund that other weak acids could effect the same phenomena. For example, treating the tetrasulfonic acid with four equivalents of lithium or sodium acetate (B = AcQ ) gave characteristic red-shifted spectra resulting from the formation of the lithium or sodium salt and four equivalents of acetic acid It wae therefore concluded that the pH of the solution (controlled by the pK, of the BH+ species) is the tnosi important factor in controlling the red-shifted behaviour of certain napbmalocyanine dyes.
With pH identified as the key factor controlling X101,, it follows that suitable IR ink formulations may be prepared by dissolving a naphtbalocyaninetetrasulfonic acid in an ink vehicle and adjusting the pH of the resulting formulation. It has been round that formulationβ having a pH within the range of 3.5 to 7, or optionally 4 to 6.5, are desirable for achieving a red-shifted Q-band while maintaining CMYK compatibility.
The pH may be adjusted using any suitable base (e.g. the conjugate bases of the weak acids described below) or using a buffer solution.
It is expected that the same phenomenon may be similarly used in controlling Q -band absorption for a whole range of sulfonated phthalocyanine and αβphthalocyanine dyes. The use of pH to One-tune Q-band absorption has not been exploited previously and represents a convenient, low cost approach to producing red-shifted IR dyes. Specific examples of dyes and formulations exploiting this phenomenon are provided below in the Examples.
The species BIT in the present invention is a week acid having a pKj in the range of 4 to 9, or optionally 4.5 to 8. The dyes of formula (I) may be readily formed by the addition of a base to the corresponding tetrasulfonic acid. The base B may be neutral (e.g. pyridine), in which case BHT will be overall positively charged (e.g. CJUjNHT). Alternatively, the base may be anionic (e.g. acetate anion) in which case BIT will be overall neutral {e.g. AcOH). In the case of any or all of BH* being neutral, the overall neutrality of the naphthalocyaninβ salt is maintained by a suitable number of metal counterions (e.g. Li", Na* etc).
The skilled person will be well aware of a wide variety of weak acids, which fulfil the criteria of the present invention. Some examples of common acids having a pKo in the range of 4 to 9 are provided below.
In accordance with convention, the pK, of some acids are referred to by their corresponding conjugate base.
For example, the pK, of pyridine refers to the pKa of the corresponding pyridinium ion.
Acetic acid 4.76
Ethyleneimine 8.01
1 H-lmidazole 6.95
2-ThiazoUmine 5.36
Acrylic acid 4.25
Mέlamine 5.00
Propanoic acid 4.86
3-Hydroxypropanoic acid 4.51
Trimethylamine oxide 4.65
Barbituric acid 4.01
AlJoxanic acid 6.64
1 •MethylimidAZOle 6.95
AJIantoin 6.96
3-Bmeooic acid 4.34 trans-Crotonic acid 4.69
3-Chlorobutanoic acid 4.05 4-Chlorobutanolc acid 4.52
Butanoic acid 4.83
2-Methylpropanoio acid 4.8S
3-Hydroxyfcutaooic acid 4.70
4-Hydroxybutanøic acid 4.72
Morpholinfi 8.33
Pyridine 5.25
2-Pyridiaamine 6.82
2,5-ΫyriΔiaeάiamine 6.43
2 ,4-Dimethylύnidazole 8.36
MethyUuccinic acid 4.13
Histamine 6.04 ; 9.75
2-Meιhylbutaooic acid 4.80
3-Methylbutaiioic acid 4.77
Pβntanoic acid 4.84
TrLmetbylβcetlc acid 5.03
2,3-Dichlorophenol 7.44
3,6-Dinicrophenύl 5.15
Pteridαne 4.05
2-Chloropbenol 8.49
3-CbJorophenol 8.85
3-Pyridioecarboxyljc acid 4 85
4-Pyhdinecarboxylic acid 4.96
2-Nitropbfti-θl 7.17
3-NJtropbenol 8-28
4-Niσopbeaol 7.15
4-Chloπ.aniline 4.15
4-Fluθroanilinc 4 65
Aniline 4.63
2-Methylpyrid«*e 5.97
3-Methylpyridioβ 5.68
4»Mβtbylpyridine 6.02
Mctboxypyridine 6.47
4,6-Diιnethylpιyrijnidioamme 4 82
3-Methylglαtaric aάά 4.24
Adipaπvic acid 4.63
Hcxanoic acid 4.85
4-MetI.ylpcntanoic acid 4.84
Benzwαidazole 5.53
Bouoic βcid 4.19
3,5-Dihydroxybenzotc acid 404 Gallic acid 441
3-Aminobenzoιc acid 4.78
2,3-Dtmethylpyridioc 6.57
2,4-Dimethytpyridine 6.99
2,5-Dύnetbylpyridine 6.40
2,6-Dimethylpyridiββ 6.65
3 ,4-DimetbylpyridiDe 6.46
3,S-Dimethy]pyridine 6.15
2-Ethylpyridine 5.89
N-Mβtbyianiline 4.84 o-Methylaniline 4.44 m-Methylani) ioe 4.73 p-Methylaniline 5.08 o-Anisidine 4.52 ro-Aaisidine 4.23 p-Aαisidine 5.34
4-Metbyithioaiuluw 4.35
Cyclohexanecarboxylic acid 4.90
Hβptanoic acid 4.89
2-MeΛylbeo2 Imidazole 6.19
Phenylacetic acid 4.28
2-(Methylaiuino)ben2oic acid 5.34
3-{Metbylamii»o)bβnzoic acid 5.10
4>(Methylainmo)benzoic acid 5.04 .
N,N-Dunβthylaniline 5.15
N-Ethylaniline 5.12
2,4,6.Triroethylpyrid-oe 7.43 oPbcBcitidine 4.43 m-Pheoeridioe 4.18 p-Phenetidiβe 5.20
Veronal 7.43
Octanedioic acid 4.52
OctaoDic acid 4.89 c-Chlorocintuwnic acid 4.23 ra-ChJorocit-oamic acid 4.29 p-ChlofOcinnamic acid 4.41
Isoquiooline 5.42
Quinoline 4.90
7-Isoquinoliool 5.68
1 •Isoquinolinamin* 7.59
3'Quinolinamine 4.91 4.44
2-Ethylbenrimidnzole 6.18
Mesitylenic acid 4.32
N-Allylaniline 4.17
Tyrosineamide 7.33
Nonanic acid 4.96
2-Methylquinoline 5.83
4-Methylquinoline 5.67
5-Metnytquiaoline 5.20
6-Methoxyquinoline 5.03 o-Metbylcinnamic acid 4.50 m-Methylcinnamic acid 4.44 p-Methylctonamic acid 4.56
4-Phenylbutanoic acid 4.76
N,N-DiethylaniliDe 6.61
PerimJdine 6.35
2 -Naphthoic add 4 17
Pilocarpine 6.87
1 , 1 O-Pbenanthroline 4.84
2.βenzylpyridine 5.13
Acridine 5.58
Phβnanthridine 5.58
Moipbine 8.21
Codeine 8.21
Papaverine 6.40
Strychnine 8.26
Brucine 8.28
It will, of course, be appreciated that the present invention is not limited to those acids Luted above and the skilled person will be readily able to select other acids (or conjugate bases) having a pK« in the range of 4 to 9, or optionally 5 to 8.
Optionally, each B is independently selected from the group consisting of a nitrogen base and an oxyanioo. Accordingly, each B may bo a nitrogen base. Alternatively, each B may be an oxyaruon base. Alternatively, there may be a mixture of nitrogen and oxyaoion bases in one dye salt. For example, the four BIT molecules may consist of two molecules of acetic acid and two pyndiniura ions, or alternatively one molecule of acetic and three imidazolium ions. The skilled person will be readily able to conceive of a variecy of mixed dye salts wiϋun the ambit of the present invention.
By "nitrogen base1' it is meant a base containing at least one nitrogen atom, which can be protonated. Optionally, the nitrogen base is a C5.l2 heteroaryl base, such as imidazole or pyridine. Imidazole is a particularly preferred base in the present invention. By αoxyanion" it is meant a base containing at least one oxyanion, which can be protonated. Optionally, the oxyanion base U a carboxyUtβ base. A carboxylate base is an organic molecule comprising at leβst one carboxylare (CO2 *) moiety. Optionally, the carboxylate base is of formula R1C(O)O", wherein Rs is selected from C|.IJ alkyl, Cs.,2 aryl or Ct n arylalkyl. Examples of carboxylate bases include acetate, benzoate etc.
The groups represented by R1 and RJ may be used for modifying or "tuning" the wavelength of Xn^ of the dye. Electron-donating substituents (e.g. alkoxy) at the ortho positions can produce a red-sbiΛ in the dye. In one preferred embodiment of the present invention, R1 and R2 are both Q.g alkoxy groups, preferably butoxy. Butoxy substituents advantageously shift the Xn^ towards longer wavelengths in the near infrared, which are preferable for detection by comπjerciaJly available lasers. In another preferred embodiment R1 and RJ are both hydrogen, which provides an expeditious synthesis of the requisite napnthalocyanioes.
The central metal atom M has been found, surprisingly, to have a very significant impact on the tight stability of the compounds of the pw&ent invention. Previously, it was believed that the nature of the organic nβphth&locysniac chromophore was primarily responsible for the rate at which such compounds degrade- However, it has now been found that certain meul αaphthalocyaninβ- show unusually high light stability compared to other metals. Specifically, gallium and copper napbthalocyanines have been shown to exhibit very good light stability, making these compounds highly suitable for αeφage and Hyperlabel™ applications in which the IR dye may be exposed to office lighting or sunlight for a year or more. Gallium compounds are particularly preferred since these have a more red-shifted A1n^ compared to copper. A more red-shifted X0^1 is preferred, because colored cyan dyes are lesβ likely to interfere with the BR dye's response to the netpage pen.
Typically A1 is a hydroxyl group (-OH). Alternatively, A1 may be selected or modified to impart specific properties onto the dye molecule. A1 may be selected to add axial siβnc bulk to the dye molecule, thereby reducing co facial interactions between adjacent dye molecules. Optionally, the axial ligand, when present, adopts a conformation (or is configured) such that it effectively "protects" or blocks a π-fβce of the dye molecule. An axial ligand, which can form an "umbrella" over the n-sysiem and reduce cofocial interactions between adjacent dye molecules is particularly suitable for use in the present invention.
It has been recognized by the present inventors that IR-absorbing dye compounds of the prior an absorb, at least to some extent, in the visible region of the spectrum. Indeed, the vast majority of IR- absorbing dye compounds known in the prior βπ are black or green or brown hues of black in the solid state. This visible absorption is clearly undesirable in "invisible" IR inks, especially IR inks for use in oetpage or Hyperlabel™ systems.
It has further been recognized by tbe present inventors that the presence of visible bands in the absorption spectra of ER-βbsorbing dye compounds, and particularly IR-absorbing metal-ligand complexes, is ac least in part due to cofacial interactions between adjacent molecules.
Typically, IR-absorbing compounds comprise a π-system which forms a substantially planar moiety in at least part of the molecule. There is a natural tendency for planar n-systems in adjacent molecules to stack on top of each other via cofacial π-interactions, known as π-π stacking. Hence, IR-absorbing compounds have a natural tendency to group together via cofacial π-interactions, producing relatively weakly bound dimβrs, (rimers etc. Without wishing to be bound by theory, it is understood by the present inventors that π-π stacking of IR-absorbing compounds contributes significantly to the production of visible absorption bands in their Ot spectra, which would not otherwise be present in the corresponding monomeric compounds. This visible absorption iε understood to be due ID broadening of IR absorption bands when π- systems stack on top of each other and π-orbitaU interact, producing small changes in their respective energy levels. Broadening of ER absorption bands Ls undesirable in two respects: firstly, it reduces the intensity of absorption in the IR region; secondly, the (R absorption band tends to tail into the visible region, producing highly coloured compounds.
Furthermore, che formation of coloured dlmers, triroers etc. via π-π interactions occurs both in the solid state and in solution. However, it ϋ a particular problem in the solid state, where there are no solvent molecules to disrupt the formation of extended π-stacked oligomers. IR dyes having acceptable solution characteristics may still be intensely coloured solids when printed onto paper. The ideal "invisible" ER. dye should remain invisible when the solvent has evaporated or wicked into the paper.
Dendrimetv, for example, are useful for exerting maximum stenc repulsion since they have a plurality of branched chains, such as polymeric chains. However, it will be appreciated from the above that any raolery or group that can interfere sufficiently with the cofacial π-π interactions of adjacent dye molecules will be suitable for minimizing visible absorption.
Alternatively (or in addition), A1 may be selected to add further hydropniliciry to the dye molecule to increase its water-dispersibility. Generally, the napbtbalocvanine dyes according to the present invention are synthesized via a cascaded coupling of four 2,3-dlcyaoonapthalene (1) molecules, although they may also be prepared from the corresponding 1-amino-3-iminoisoindolene (2).
Figure imgf000016_0001
The cascaded base-catalysed macrocycusation may be facilitated by metal templating, or it may proceed In the absence of a metal. If macrocylisanon it performed in the absence of a lemplaαng metal, then a metal may be readily inserted into the resultant metal-free napthalocyanine. Subsequent sulfonation and salt formation proceed by standard procedures. Further synthetic details are provided below in the Examples.
The term "hydrocarbyl" is used herein to refer to monovalent groups consisting generally of carbon and hydrogen. Hydrocarbyl groups thus include alkyl, alkenyl and alkynyl groups (in both straight and branched chain forms), carbocycuc groups (including polycycloalkyl groups such as bicyclooctyl and adamantyl) and aryl groups, and combinations of the foregoing, such as alkylcycloalkyl, alkylpolycycloalkyl, alkylaryl, alkenyUryl, alkvnylaryl, cycloalkylaryl and cycloalkenylaryl groups. Similarly, the term "bydrocarbylene" refers to divalent groups corresponding to the monovalent hydrocarbyl groups described above. Unless specifically stated otherwise, up to four -C-C- and/or -C-H moieties in the hydrocarbyl group may be optionally interrupted by one or more moieties selected from -O-; -NR"-; -S-; -C(O)-; -C(O)O-; -C(O)NR"-; -S(O)-; -SO2-; -SO2O-; -SOjNR1"-; where R* is β group selected from H, CM1 alky], C6., 2 aryl or C6-I2 arylalkyl. Urϋeϋ specifically stated otherwise, where the hydrocarbyl group contains one or more -C=C- moieties, up to four -C-C- moieties may optionally be replaced by -C=N-. Hence, the terra "hydrocarbyl" may include moieties such as heteroaryl, ether, thioetfaer, carboxy, hydroxy I, alkoxy, amine, thiol, amide, ester, ketone, sulfoxide, sulfonate, sulfonamide etc.
Unless specifically stated otherwise, the hydrocarbyl group ruay comprise up to four subsdtuents independently selected from halogen, cyano, nitro, a hydroptulic group aa defined above (e.g. -SOjH, -SOjK, -CO2Na, -NH3 *, -NMe/ etc.) or a polymeric group as defined above (e g a polymeric group derived from polyethylene glycol).
The term "aryl" is used herein to refer to an aromatic group, such as phenyl, naphthyl or oriprycenyl. Ci-it aryl, for example, refers to an aromatic group having from 6 to 12 carbon atoms, excluding any subsάcueDts. The term "aryiene", of course, refers to divalent groups corresponding to the monovalent aryl groups described above. Any reference to aryl implicitly includes aryiene, where appropriate.
The term "heteroaryl" refers to an aryl group, where 1 , 2, 3 or 4 carbon atoms are replaced by a heteroatom selected from N, O or S. Examples of heteroaryl (or heteroaroraβtic) groups include pyridyl, benzinύdazolyl, indazolyl, quinolinyl, isoquinolinyl, indoUnyl, isoindolinyl, indolyl, ύoindolyl, ruranyl, ihiophenyl, pyrrolyl, thlazoly), imidazotyl, oxaiolyl, isoxazolyl, pyrazolyl, isoxazolonyl, piperazinyl, pyrimidLnyl, piperidinyl morphollnyl, pyrrolidinyl, ϋothiazolyl, triazolyl, oxadiazolyl, tbiadiazolyl, pyridyl, pyrimidinyl, benzopyriroidinyl, benzotriazole, quinoxalinyl, pyridazyl, coumarinyl etc. The term "heteroarylene", of course, refers to divalent groups corresponding to the monovalent heteroaryl groups described above. Any reference to beteroaryt implicitly includes beteroarylene, where appropriate. Unless specifically stated otherwise, aryl, aryiene, beteroaryl and beteroarylene groups may be optionally substituted with 1 , 2, 3, 4 or 5 of the substitueius described below.
Where reference is made to optionally substituted groups (e.g. in connection with bridged cyclic groups, aryl groups or heteroaryl groups), the optional subsuruenr(9) are independently selected from Ct4j alkyl, C1-3 alkoxy, -(OCH.CH^OR1* (wherein d ifl an integer from 2 to 5000 and KJ U H, C14 alkyl or C(O)C1.* alkyl), cyano, halogen, amino, hydroxyl, thiol, -SR', -NR"RV, nitro, phenyl, phenoxy, -CO2R', -C(O)R', -OCOR". -SO2R', -OSO2R', -SO2OR", -NHC(O)R', -CONR-R", -CONR"R", -SOJNR"R\ wherein R" and R' are independently selected from hydrogen, Ci.u alky), phenyl or pheny|-C|.β aHcyl (e.g. benzyl). Where, for example, a group contains more than one substituent, different substituenU can have different R" or R' groups. For example, a naphthyl group may be substituted with three subsoruenrs: - SO2NHPh. -CO2Me croup and -NH2.
The term "alley r is used herein to refer to alkyl groups in both straight and branched forms, The alkyl group may be interrupted with 1 , 2 or 3 heteroatoras selected from O, N or S. The alkyl group may also be interrupted with 1 , 2 or 3 double and/or triple bonds. However, the term "alkyl" usually refers to alkyl groups having no heteroatom interruptions or double or triple bond interruptions. Where "alkenyl" groups are specifically mentioned, this is not mieoded to be construed as a limitation on the definition of "alkyl" above. The term "alky)" also includes balogenoalkyl groups. A C,.n alkyl group may. for example, have up to 5 hydrogen atoms replaced by halogen atoms. For example, ibe group -OC(O)CM2 aUO'l specifically includes -OC(O)CF3. Where reference is made to, for example, C\.n alkyl, it is meant the alkyl group may contain any
Dumber of carbon atoms between 1 and ) 2. Unless specifically stated otherwise, any reference to "alley)" means C|.,2 alkyl, preferably C1^ alkyl.
The tern "alkyl" also includes cycloalkyl groups. As used herein, the term "cycloelkyl" includes cycloαtkyl, polycycloalkyl, and cycloalkβny) groups, as well as combinations of these with linear alkyl groups, such as cycloalkylalky) groups. The cycloalkyl group may be interrupted with 1 , 2 or 3 beteτoatoms selected from O, N or S. However, the term "cycloalkyl" usually refers to cycloalkyl groups having no heteroatom interruptions. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cyclohexenyl, cyclohexylmeihyl and adamancyl groups.
The term "arylalkyt" refers to groups such aa benzyl, phenylethyl and naphihylmetbyl. The term "halogen" or "halo" is used herein to refer to any of fluorine, chlorine, bromine and iodine.
Usually, however, halogen refers to chlorine or fluorine substituents.
Where reference is made to "a substituent comprising ..." (e.g. "a substitueoi comprising a nydrophilic group", "a substitueot comprising an acid group (including salts thereof)", "a substituent comprising a polymeric chain" etc.), the substituent io question may consist entirely or partially of the group specified. For example, "a substituent comprising an acid group (including salts thereof)" may be of formula -{CH^J-SOJK, wherein j is O or an integer from 1 to 6. Hence, in this context, the term "subatituenr" may be, for example, an alkyl group, which has a specified group attached. However, it will be readily appreciated that the exact nature of the substituent is not crucial to the desired functionality, provided that the specified group is present Chiral compounds described herein have not been given stereo-descriptors. However, when compounds may exist LD stereoisorααric forms, then all possible stereoisomers and mixtures thereof are included (e.g. enantiomers, diastereomer≤ and all combinations including racemic mixtures etc.).
Likewise, when compounds may exist in α number of regioisomeric forms, then all possible regioisomers and mixtures thereof are included. For the avoidance of doubt, the term "a" (or "an"), in phrases such as "comprising a", means "at least one", and not "one and only one". Where Ibe term "at least one" is specifically used, this should not be construed as having a limitation on the definition of "a".
Throughout the specification, the term "comprising", or variations such as "comprise" or "comprises", should be construed as including a stated element, integer or step, but not excluding any other element, integer or step.
Inkiet Inks
The present invention also provides an inkjet ink. Preferably, the inkjet ink is a water-baaed inkjet ink. Water-based inkjet ink compositions are we U known in the literature and, is addition to water, may comprise additives, such as co-solvents, biocides, sequestering agents, bumectants, viscosity modifiers, penetrants, wetting agents, surfactants etc.
Co-solvents are typically water-soluble organic solvents. Suitable water-soluble organic solvents include C1-4 alkyl alcohols, sucb as ethanol, methanol, butanoL, propanol, and 2-propanol, glycol ethers, sucb as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol raono-isopropyl ether, diethylene glycol mono- isopropyl ether, ethylene glycol mono-n-butyl etheT, dieihylene glycol mono-n-butyl ether, methylene glycol tαoDo-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-buryl ether, 1 -methyl- 1- metnoxybutanol, propylene glycol monoinetbyl ether, propylene glycol roonoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, dipropylene glycol monoraethyl etner, dipropylene glycol monoethyl ether, dipropylene glycol mono-n- propyl ether, dipropylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-buryl ether; forraamide, acetaroide, dimethyl sulfoxide, sorbitol, sorbitan, glycerol monoacet-ite, glycerol diacetate, glycerol triacetate, and sulfolane; or combinations thereof.
Other useful water-soluble organic solvents include polar solvents, such as 2-pyrrolidone, N- methylpyrrolidone, ε-caprolacram, dimethyl sulfoxide, sulfolane, morpholine, N-etbylrαorpholine, 1-3- dimetbyl-2-imjdA-θliduκme and combination- thereof. The InkJet ink may contain a high-boiling water-soluble organic solvent which can serve as a wetting agent or humectant for imparting water rctenήvity and wetting properties to the ink composition. Such a high-boiling water-soluble organic solvent includes one having a boiling point of 180°C or higher. Examples of the water-soluble organic solvent having a boiling point of 180°C or higher are ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene- 1 ,4-diol, 2-ethyt- 13-hexanedιol, 2-methyl-2,4-pentanediol, tripropylene glycol monoraethyl ether, dipropylene glycol monoethyl glycol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, triethylene glycol monomethyl ether, teσaethylene glycol, methylene glycol, dietbylcne glycol monoburyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, tripropylene glycol, polyethylene glycols having molecular weights of 2000 or lower, 1 ,3 -propylene glycol, isopropylene glycol, isobutylene glycol, 1 ,4-butanediol, 1 ,3-butanedioL, 1,5-pentanediol, 1,6-hexanediol, glycerol, erythhtol, pentaerythritol and cornbinations thereof.
The total water-soluble organic solvent content in the inkjet ink is preferably about 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total ink composition.
Other suitable wetting agents or bumectants include saccharides (including monosaccharides, oligosaccharides and polysaccharides) and derivatives thereof (e.g. malotol, sorbitol, xyLttol, hyaluronic salts, aldonic acids, uronic acids etc.)
The inkjet ink may also contain a penetrant for accelerating penetration of the aqueous ink into the recording medium. Suitable penetrants include pojyhydric alcohol alkyl ethers (glycol ethers) and/or 1 ,2- alkyldiok Examples of suitable polyhydric alcohol alkyl ethers are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono-n-propyl emer, ethylene glycol monc-isopropyl ether, dietbylene glycol mono-isopropyl ether, ethylene glycol mouo- D-buryl ether, diethylene glycol mono-n-butyl ether, methylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, dietbylene glycol monø-t-buιyl ether, 1 -methyl- 1-methoxybuianol, piopylene glycol monomethyl ether, propylene glycol moooethyl ether, propylene glycol mono-i-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-lεopropyl ether, dipropytene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono* isopropyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-buryl ether. Examples of suitable 1 ,2-alkyldiols are 1,2-pentanediol and 1 ,2-hexaoediol. The penetraiu may also be selected from straight-chain hydrocarbon diols, such as 13-propanediol, 1,4-bιuanedioL, 1 ,5-pentanediol. 1 ,6-hexanediol, 1,7-beptanediol, and 1,8-ocranediol. Glycerol or urea may also be used as penetrants.
The amount of penetrant is preferably in the range of l to 20% by weight, more preferably 1 to 10% by weight, based on the total ink composition.
The inkjet ink may also contain a surface active agent, especially an anionic surface active agent and/or a noniooic surface active agent. Useful anionic surface active agents include sulfonic acid types, such as alkanesulibnic acid salts, α-olefinsulfouic acid salts, alkylbenzenesulfonic acid salts, alkylnapbthaleαesuUbnic acids, acylmethyltaurines, and dialkyisulfosuccinic acids; alkylsuLforic ester salts, sulfated oils, sulfated olefins, polyoxyetbylene alkyl ether sulfurio ester salts; carboxyUc acid types, e.g., fatty acid salts and alkylsarcostne salts, and phosphoric acid ester types, such as alkylpbospboric ester salts, polyoxyeibylene alky) etbor phosphoric ester salts, and glycerophosphoric ester salts. Specific examples of the anionic surface active agents are sodium dodecylbenzenesulfonate, sodium laurate, and a polyoxyethyleae alkyl ether sulfate ammonium salt
Suitable non ionic surface active agents include ethylene oxide adduct types, such as polyoxyetbylcne alkyl etherβ, polyoxyethyleue alkylphenyl ethers, polyoxyethylβoe alkyl esters, and polyoxyethylene aUcylamides; polyol eater types, such as glycerol alkyl esters, sorbitan alkyl esters, and sugar alkyl esters; polyeiber types, such as polyhydric alcohol alky) ethers; and alkanoUnude types, such as alkanolamine (airy acid amides. Specific examples of nonionic surface active agents are ethers such aβ polyoxyethylene nonylphenyl ether, polyoxyetbylene octylphenyl eiher, polyoxyethylene dodccylphenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyalkylene alkyl ethers (e.g. polyoxyetbylene alky) ethers); and esters, such as polyoxyethylene oleate, polyoxyethylene oleate ester, polyoxyethylene distearate, sorbitao laurate. sorbican monostearate, sorbitgo mono-oleare, sorbitan scsquioleate, polyoxyeihylene mono-oleate, and polyoxyethylcoc stearβte. Acetylene glycol surfece active agents, such as l^J^-ietramethyl-5-decyne^J-diol, 3,6-dunethyN4-octyne-3,6-diol or 3,S-dimethyl-1-hexvn-3-ol. may also be used
The inkjet ink may also include a biocide. such as benzoic acid, dichloropbene, hexachlorophene, sorbic acid, bydroxybenzoic esters, sodium dehydroacetate, 1 -2-benthiazolu>3-onfl, 3,4>isothiazolin-3-ooe or 4,4-dimethyloxazolidine.
The inkjet ink may also contain a sequestering agent, auch as emylenediamineietraacetic acid (EDTA).
The inkjet ink may also contain a singlet oxygen quencher. The presence of singlet oxygen quencheτ(s) in the ink reduces the propensity for the tR-absorbing dye to degrade. The quencher consumes any singlet oxygen generated in the vicinity of the dye molecules and, hence, minimizes iheir degradation. An excels of singlet oxygen quencher is advantageous for minimizing degradation of the dye and retaining its JR-absorbing properties over time. Preferably, the singlet oxygen quencher is selected from ascorbic acid, 1,4-diazabicyclo-[2.2.2]ocrane (DABCO), azides (eg. sodium azide), histidinβ or tryptophan.
InkJet Printers
The present invention also provides an inkjet printer comprising a printhead in fluid communication with at least one ink reservoir, wherein said ink reservoir comprises an inkjet ink as described above.
InkJet printers, such as thermal bubble-jet and piezoelectric printers, are well known in the art and will form part of the skilled person's common general knowledge. The printer may be a high-speed inkjet printer. The printer is preferably a pagewidth prinier. Preferred inkjet printers and printheads for use in che present invention are described in the following patent applications, all of which are incorporated herein by reference in their entirety.
10/302,274 6692108 6672709 10/303,348 6672710 6669334
10/302,668 10/302,577 6669333 10/302,618 10/302,617 10/302,297
Printhead
A rvfemjet printer generally has two printhead integrated circuits that are mounted adjacent each other to fomi a pagewidth printhead. Typically, the printbead ICs can vary in size from 2 inches to 8 inches, so several combinations can be used to produce, say, an A4 pagewidth printhead. For example two printhead ICs of 7 and 3 inches, 2 and 4 inches, or S and 5 inches could be used to create an A4 printhead (the notation is 7:3). Similarly 6 and 4 (6:4) or 5 and 5 (5:5) combinations can be used. An A3 printhead can be constructed from 8 and 6-incb printhead integrated circuits, for example. For photographic printing, particularly in camera, smaller printbeads can be used. It will also be appreciated that a single princh&ad integrated circuit, or more than two such circuits, can also be used to achieve (be required printbead width. A preferred prinmead embodiment of the pinthead will now be described with reference to Figures
17 and 18. A printhead 420 takes the form of an elongate unit. As best shown in Figure 18, the components of the printbead 420 include a support member 421 , a flexible PCB 422, an ink distribution molding 423, an ink distribution plate 424, a MEMS printhead comprising first and second printhead integrated circuits OCs) 425 and 426, and busbars 427. The support member 421 is can be formed from any suitable material, such aa metal or plastic, and can be extruded, molded or formed in any other way. The support member 421 should be strong enough TO hold the other components in the appropriate alignment relative to each other whilst stiffening and strengthening the printhead as a whole.
The flexible PCB extends the length of the printhead 420 and includes first and second electrical connectors 428 and 429. The electrical connectors 428 and 429 correspond with flexible connectors (not shown). The electrical connectors include contact areas 450 and 460 that, in use, are positioned in contact with corresponding output connectors from a SoPEC chip (not shown). Data from the SoPEC chip posses along the electrical connectors 428 and 429, and is distributed to respective ends of the fust and εecond printhead ICs 425 and 426. Af shown in Figure 19, the ink distribution molding 423 includes a plurality of elongate conduits
430 that distribute fluids (ie, colored inks, infrared ink and fixative) and pressurized air from the air pump 20 along the length of the printhead 420 (Figure \ 8). Sets of fluid apertures 431 (Figure 20) disposed along the length of the ink distribution molding 423 distribute the fluids and air from the conduits 430 to the ink distribution plate 424. The Quids and air are supplied via nozzles 440 formed on a plug 441 (Figure 21), which plugs into a corresponding socket (not shown) in the printer. The distribution plate 424 is a multi-layer construction configured to take fluids provided locally from the fluid apertures 431 and distribute them through smaller distribution apertures 432 into the pnnthead ICs 425 and 426 (as shown in Figure 20).
The printhead ICs 425 and 426 are positioned end to end, and are held in contact with the distribution plate 424 so that ink from the smaller distribution apertures 432 can be fed into corresponding apertures (not shown) in the printhead ICs 425 and 426.
The busbars 427 are relatively high-capacity conductors positioned to provide drive current to the actuators of the printhead nozzles (described in detail below). As best shown in Figure 20, the busbars 427 are retained in pom-ion at one end by a socket 433, and at both ends by wrap-around wings 434 of the flexible PCB 422. The busbars also help hold the printhead ICs 425 in position. As shown best in Figure 18, when assembled, the flexible PCB 422 is effectively wrapped around the other components, thereby holding them in contact with each other. Notwithstanding this binding effect, the support member 421 provides a major proportion of the required 9tifihesε and strength of the printhead 420 as a whole.
Two forms of printhead nozzles ("thermal bend actuator" and "bubble forming heater element actuator"), suitable for use in the printhead described above, will now be described
Thermal Bend Actuator
In the thermal bend actuator, there is typically provided a nozzle arrangement having a nozzle chamber containing ink and a thermal bend actuator connected to a paddle positioned within the chamber. The thermal actuator device is actuated so as to eject ink from the nozzle chamber The preferred embodiment includes a particular thermal bend actuator which includes a series of tapered portions for providing conductive hearing of a conductive (race. The actuator is connected to the paddle via an arm received through a slotted wall of the nozzle chamber. The actuator arm has a mating shape so as to mate substantially with the surfaces of the slot in the nozzle chamber wall. Turning initially to Figures 22(a)-(c), there is provided schematic illustrations of the basic operation of a nozzle arrangement of this embodiment. A nozzle chamber 501 is provided filled with ink S02 by means of an ink inlet channel 503 which can be etched through a wafer substrate on which the nozzle chamber 501 rests. The nozzle chamber S0 I further includes an ink ejection port 504 around which an Ink meniscus forms. Inside the nozzle chamber 501 is a paddle type device 507 which is interconnected to an actuator
508 through a slot in me wall of the nozzle chamber 501. The actuator 508 includes a beater means e.g. 509 located adjacent to an end portion of a post 510. The post 510 is fixed to a substrate.
When it is desired to eject a drop from the nozzle chamber 501 , as illustrated in Figure 22(b), the heater means 509 is heated so as to undergo thermal expansion. Preferably, the beater means 509 itself or the other portions of the actuator 508 are built from materials having a high bend efficiency where the bend efficiency is defined as:
Figure imgf000023_0001
A suitable material for the boater elements U a copper nickel alloy which can be formed so as to bend a glass material.
The beater means 509 is ideally located adjacent the end portion of the poet 510 such that (be effects of activation are magnified at the paddle end S07 such that small thermal expansions near the post 5 I0 result in large movements of the paddle end.
The beater means 509 and consequential paddle movement causes a general increase in pressure around the ink meniscus 505 which expands, as illustrated in Figure 22{b), in a rapid manner The beater current is pulsed and ink is ejected out of the port 504 in addition to flowing in from the ink channel 503. Subsequently, the paddle 507 is deactivated to again return to its quiescent poβiu'on. The deactivation causes a general reflow of the ink into the nozzle chamber. The forward momentum of the ink outside the nozzle rim and the corresponding backflow results in a general necking and breaking off of the drop 512 which proceeds to the print media. The collapsed meniεous 505 results in a general sucking of ink into the nozzle chamber 502 via tbe ink flow channel 503. In time, me nozzle chamber 501 is refilled such that tbe position in Figure 22(a) U again reached and the nozzle chamber is subsequently ready for the ejection of another drop of ink.
Figure 23 illustrates a side perspective view of the nozzle arrangement. Figure 24 illustrates sectional view through an array of nozzle arrangement of Figure 23. In these figures, the numbering of elements previously introduced has been retained. Firstly, the actuator 508 includes a series of tapered actuator units e.g. 515 which comprise an upper glass portion (amorphous silicon dioxide) 516 formed on top of a titanium nitride layer 517. Alternatively a copper nickel alloy layer (hereinafter called cupronickel) can be utilized which will have a higher bend efficiency.
Tbe titanium nitride layer 517 is in a tapered form and, as such, resistive hearing takes place near an end portion of the post 510. Adjacent titanium nitride/glass portions 51S are interconnected at a block portion 519 which also provides a mechanical structural support for the actuator 503.
The heater means 509 ideally includes a plurality of the tapered actuator unit 515 which are elongate and spaced apart such that, upon beating, tbe bending force exhibited along the axis of the actuator 508 is maximized. Slots are defined between adjacent tapered units 515 and allow for slight differential operation of each actuator 508 with respect to adjacent actuators 508.
The block portion 519 is interconnected to an arm 520. Tbe arm 520 is in turn connected to the paddle 507 inside the nozzle chamber 501 by means of a slot e.g. 522 formed in the side of the nozzle chamber 501. Tbe slot 522 ia designed generally to mate with the surfaces of the arm 520 so as to minimize opportunities for the outflow of ink around the arm 520. The ink is held generally within the nozzle chamber 501 via surface tension effects around the slot 522.
When it is desired to actuate the arm 520, a conductive current is passed through the titanium nitride layer 5)7 via viae within the block portion 519 connecting to a lower CMOS layer 506 which provides tbe necessary power and control circuitry for the nozzle arrangement. The conductive current results in beating of the nitnde layer 517 adjacent to the post 510 which results in a general upward bending of the arm 20 and consequential ejection of ink out of the nozzle 504. The ejected drop is printed on a page in the usual manner for an inkjet printer as previously described.
Aa array of nozzle arrangements can be formed so as to create a single printhead. For example, in Figure 24 there is illustrated a partly sectioned various array view which comprises multiple ink ejection nozzle arrangements of Figure 23 laid out in interleaved lines so as to form a priotbead array. Of course, different types of arrays can be formulated including nil I color arrays etc.
The construction of the primhead system described can proceed utilizing standard MEMS techniques through suitable modification of the steps as set out in US 6,243,113 entitled 'image Creation Method and Apparatus (U 41)" to th« present applicant, the contents of which are fully incorporated by cross reference.
Bubble Forming Heaier Element Actuator
With reference to Figure 17, the unit cell 1001 of a bubble forming heater element actuator comprises a nozzle plate 1002 with nozzles 1003 therein, the nozzlea having nozzle rims 1004, and apertures 1005 extending through the nozzle plate. The nozzle plate 1002 is plasma etched from a silicon nitride structure which is deposited, by way of chemical vapor deposition (CVD), over a sacrificial material which is subsequently etched.
The prinrhead also includes, with respect to each nozzle 1003, side walls 1006 on which the nozzle plate is supported, a chamber 1007 defined by the walls and the nozzle plate 1002, a multi-layer substrate 1006 and an inlet passage 1009 extending through the multi-layer substrate to the far side (not shown) of the substrate. A looped, elongate heater element 1010 is suspended within the chamber 1007, so that the element is in the form of a suspended beam. The pnnthead as shown is a raicroeleciromechanical system (MEMS) structure, which is formed by a lithographic process.
When the printhead is in use, ink IOU from a reservoir (not shown) enters the chamber 1007 via the inlet passage 1009, so that the chamber fills. Thereafter, the heater element 1010 is heated for somewhat less than 1 micro second, 9o that the beating is in the form of a thermal pulse. It will be appreciated that the beater element 1010 is in thermal contact with the ink 1011 in the chamber 1007 60 that when the element is heated, this causes the generation of vapor bubbles in the ink. Accordingly, the ink 101 1 constitutes a bubble forming liquid. The bubble 1012, once generated, causes an increase in pressure within the chamber 1007, which in turn causes the ejection of a drop 1016 of the ink 10) 1 through the nozzle 1003. The rim 1004 assists in directing the drop 1016 as it is ejected, so as to minimize the chance of a drop misdirection.
The reason that there is only one nozzle 1003 and chamber 1007 per inlet passage 1009 is so that the pressure wave generated within the chamber, on heating of the element 1010 and forming of a bubble 1012, does not effect adjacent chambers and their corresponding nozzles.
The increase in pressure within the chamber 1007 not only pushes ink 1011 out through the nozzle 1003, buc also pushes some ink back through the inlet passage 1009. However, the inlet passage 1009 iε approximately 200 to 300 microns in length, and is only approximately 16 microtis in diameter. Hence there is a substantial viscous drag. A9 a result, the predominant effect of the pressure rise in the chamber 1007 is to force ink out through the nozzle 1003 as an ejected drop 1016, rather than back through the inlet passage 9. As shown in Figure 17, the ink drop 1016 is being ejected is shown during its "necking phase" before the drop breaks off. At this stage, the bubble 1012 has already reached its mavimnm size and has then begun to collapse towards the point of collapse 1017.
The collapsing of the bubble 1012 towards the point of collapse 1017 causes some Ink 1011 to be drawn from within the nozzle 1003 (from the sides 1018 of the drop), and some to be drawn from the inlet passage 1009, towards the point of collapse. Most of the ink 1011 drawn in this manner is drawn from the nozzle 1003. forming an annular neck I Ol 9 at the base of the drop 16 prior to its breaking off.
The drop 1016 requires a certain amount of momentum to overcome surface tension forces, in order to break off. As ink 1011 is drawn from the nozzle 1003 by the collapse of the bubble 1012, the diameter of the neck 10)9 reduces thereby reducing the amount of total surface tension holding the drop, so that the momentum of the drop as it is ejected out of the nozzle is sufficient to allow the drop to break off.
When the drop 1016 breaks off, cavitation forces are caused as reflected by the arrows 1020, as the bubble 1012 collapses to the point of collapse 1017. It will be noted that mere are no solid surfaces in the vicinity of the point of collapse 1017 on which the cavitation can have an effect
InkJet Cartridges
The present invention also provides an inkjet ink cartridge comprising an inkjet ink as described above. Ink cartridges for inkjet printers are well known in the art and are available in numerous forms. Preferably, the inkjet ink cartridges of the present invention are replaceable. InkJet cartridges suitable for use in the present invention are described in the following patent applications, all of which are incorporated herein by reference in their entirety.
6428155, 10/171,987
In one preferred form, the ink cartridge comprises: a housing defining a plurality of storage areas wherein at least one of the storage areas contains colorant for printing information that is visible to the human eye and at least one of the other storage areas contains an inkjet ink as described above.
Preferably, each storage ansa is sized corresponding to the expected levels of use of its contents relative to the intended print coverage for a number of printed pages.
There now follows a brief description of an ink cartridge according to me present invention. Figure 12 shows the complete assembly of the replaceable ink cartridge 627. It has bladders or chambers for storing fixative 644, adhesive 630, and cyan 631. magenta 632, yellow 633, black 634 and infrared 635 inks. The cartridge 627 also contains a micro air Oiler 636 in a base molding 637. As shown in Figure 9, the micro air filler 636 interfaces with an air pump 638 inside the printer via a hose 639. This provides filtered air to the printheads 70S to prevent ingress of micro particles into the Memjet™ printheads 705 which may clog the nozzles. By incorporating the aix filter 636 within the cartridge 627, the operational life of the filter is effectively linked to the life of the cartridge. This ensures that the filter is replaced together with die cartridge rather then relying on the user to clean or replace the filter at the required intervals. Furthermore, the adhesive and infrared ink are replenished together with the visible inks and air filter thereby reducing how frequently me printer operation iβ interrupted because of the depletion of a consumable material. The cartridge 627 has a thin wall casing 640. The ink bladders 631 to 63 S and fixitive bladder 644 are suspended within the casing by a pin 645 which books the cartridge together. The single glue bladder 630 is accommodated in tb« base molding 637. This is a folly recyclable product with a capacity for printing and gluing 3000 pages (1500 sheets).
Substrates As mentioned above, the dyes of the present invention are especially suitable for use in
Hyperlabel™ and neipage systems. Such systems are described in more detail below and in the patent applications listed above, all of which are incorporated herein by reference in their entirety.
Hence, the present invention provides a substrate having an IR-absorbing dye as described above disposed thereon. Preferably, the substrate comprises an interface surface. Preferably, the dye is disposed in the form of coded data suitable for use in netpage and/or Hyperlabel™ systems. For example, the coded data may be indicative of the identity of a product item. Preferably, the coded data is disposed over a substantial portion of an interface surface of the substrate (e.g. greater man 20%, greater than 50% or greater than 90% of the surface).
Preferably, the substrate is IR reflective so that the dye disposed thereon may be detected by a sensing device. The substrate may be comprised of any suitable material such as plastics (e g polyolefinβ, polyesters, polyamides etc.), paper, metal or combinations thereof.
For netpage applications, the substrate is preferably a paper sheet. For Hyperlabel™ applications, the substrate is preferably a tag, a label, a packaging material or a surface of a product item Typically, tags and labels are comprised of plasties, paper or combinations thereof. In accordance with Hyperlabel™ applications of the invention, the substrate may be an interactive product item adapted for interaction with a user via a sensing device and a computer system, the interactive product item comprising: a product item having an identity; an interface surface associated with the product item and having disposed thereon information relating to the product item and coded data indicative of the identity of the product item, wherein said coded data comprise an IR-absorbing dye as described above.
Netpaee and Hvperlahel™
Netpage applications of this invention are described generally in the sixth and βeventh aspects of the invention above. Hyperlabel™ applications of this invention are described generally in the eighth and ninth aspects of the invention βbovc.
TheTβ now follows a detailed overview of nctpage and Hyperiabel™. (Note. Memjet™ and Hyperlabel™ are trade marks of Silveibrook Research Pty Ltd, Australia). It will be appreciated that not every implementation will necessarily embody all or even most of the specific details and extensions discussed below in relation to tbβ basic system. However, the system is described in its most complete form to reduce the need for external reference when attempting to understand the context in which the preferred embodiments and aspects of the present invention operate.
In brief summary, the preferred form of the netpage system employs a computer interface in the form of a mapped surface, that is, a physical surface wbicb contains references to a map of the surface maintained in a computer system. The map references can be queried by an appropriate sensing device.
Depending upon the specific implementation, the map references may be encoded visibly or invώibly, and defined La such a way that a local query oo the mapped surface yields an unambiguous map reference both within the map and among different maps. The computer system can contain information about features on the mapped surface, and such information can be retrieved based on map references supplied by a sensing device used with the mapped surface. The information thus retrieved can take the form of actions which are initialed by the computer system on behalf of the operator in response to the operator's interaction with the surface features.
In its preferred form, the netpage system relies on the production of, and human interaction with, netpages. These are pages of text, graphics and images printed on ordinary papor, but which work like interactive web pages. Information is encoded on each page using ink which is substantially invisible to the unaided human eye. The ink, however, and thereby the coded data, can be sensed by an optically imaging pen and transmitted to the netpage system.
In the preferred form, active buttons and hyperlinks on each page can be clicked with the pen to request ioformatioo from the network or to signal preferences to a network server. In one embodiment, text written by hand on a netpage is automatically recognized and converted to computer text in the netpage system, allowing forms to be filled in. In other embodiments, signatures recorded on a netpage are automatically verified, allowing e-conuaerce transactions to be securely authorized.
As illustrated in Figure 1, a printed netpage 1 can represent an interactive form which can be filled in by the user both physically, on the printed page, and "electronically", via communication between the pen and the netpage system. The example shows a "Request" form containing name and address fields and a submit button. The netpage consists of graphic data 2 printed using visible ink, and coded data 3 printed as a collection of rags 4 using invisible ink. The corresponding page description 5, stored on the netpage network, describes the individual elements of the netpage. In particular it describes the type and spatial extern (zone) of each interactive element (i.e. text field or burton in the example), to allow the netpage system to correctly interpret input vie the netpage. The submit button 6, for example, has a zone 7 which corresponds to the spatial extent of the corresponding graphic 8.
As illustrated in Figure 2, the netpage pen 101, a preferred form of which is shown in Figures 6 and 7 and described in more detail below, works in conjunction with a personal computer (PC), Web terminal 75, or a netpage printer 601. The netpage printer ύ an Interne t-coαoec ted printing appliance for home, office or mobile use. The pen is wireless and communicates securely with toe nerpage network via a short-range radio link 9. Short-range communication is relayed to the netpage network by a local relay function which is cither embedded in the PC, Web terminal or nctpace printer, or is provided by a separate relay device 44. The relay function can also be provided by a mobile phone or other device which incorporates botb short-range and longer-range communications functions.
In an alternative embodiment, the netpage pen utilises a wired connection, such as a USB or other serial connection, to the PC, Web terminal, netpage printer or relay device.
The netpage printer 601 , a preferred form of which Is shown In Figures 9 to 11 and described In more detail below, is able to deliver, periodically or on demand, personalized newspapers, magazines, catalogs, brochures and other publications, all printed at high quality as interactive netpages. Unlike a personal computer, the nerpage printer is an appliance which can be, for example, wall-mounted adjacent to an area where the morning news is first consumed, such as in a user's kitchen, near a breakfast table, or near the household's point of departure for the day. It also comes in tabletop, desktop, portable and miniature versions.
Neipageε printed at their point of consumption combine the oase-of-use of paper with the timeliness and interactivity of an interactive medium. Au shown in Figure 2, the netpage pen 101 interacts with the coded data oo a printed netpage 1 (or product item 201) and communicates the interaction via a short-range radio link 9 to a relay. The relay sends the interaction to the relevant netpage page server 10 for interpretation. In appropriate circumstances, the page server sends a corresponding message to application computer software running on a netpage application server 13. The application server may in turn send a response which is printed on the originating printer.
In an alternative embodiment, the PC, Web terminal, netpage printer or relay device may communicate directly with local or remote application software, including a local or remote Web server Rclatedly, output is not limited to being printed by the netpage printer. It can also be displayed on the PC or Web terminal, and further interaction can be screen-based rather than paper-based, or a mixture of the two. The Qctpagc system is made considerably more convenient in the preferred embodiment by being used in conjunction with high-speed roicroelectromechanjcal system (MEMS) based inkjβt (Memjet™) printers. In the preferred form of this technology, relatively high-speed and high-quality printing is made more affordable to consumers. In its preferred form, a netpage publication has the physical characteristics of a traditional newsmagazine, such as a set of letter-size glossy pages printed in full color on bom sides, bound together for easy navigation and comfortable handling.
The netpage printer exploits the growing availability of broadband Internet access. Cable service is available to 95% of households in the United States, and cable modem service offering broadband Internet access is already available to 20% of these. The netpage printer can also operate with slower connections, but with longer delivery times and lower image quality. Indeed, the netpage system can be enabled using existing consumer inkjet and laser printen., although the system will operate more slowly and will therefore be lesβ acceptable from a consumer's poiot of view. In other embodiments, the netpage system is hosted oo a private intranet. In still other embodiments, the netpage system is boated on a single computer or computer-enabled device, such as a printer.
Netpage publication servers 14 on the netpage network are configured to deliver print-quality publications to netpage printer.. Periodical publications are delivered automatically to subscribing netpage printers via pointcasting and multicasting Internet protocols. Personalized publications are filtered and formatted according to individual user profiles.
A oetpage printer can be configured to support any number of pens, and a pen can work with any number of netpage printers. In the preferred implementation, each netpage, pen has a unique identifier. A household may have a collection of colored netpage pens, one assigned to each member of the family. This allows each user to maintain a distinct profile with respect to a netpage publication server or application server.
A netpage pen con also be registered with a netpage registration server 11 and linked to one or more payment card accounts. This allows e-commerce payments to be securely authorized using the netpage pea The netpage registration server compares the signature captured by the netpage pen with a previously registered signature, allowing it to authenticate the user's identity to an e-commerce server. Other biometrics can also be used to verily identify. A version of the nerpage pen includes fingerprint scanning, verified in a similar way by the oetpage registration server.
Although a oetpage primer may deliver periodicals such as the morning newspaper without user intervention, it can be configured never to deliver unsolicited junk mail. In its preferred form, it only delivers periodicals from subscribed or otherwise authorized sources. In this respect, the netpage printer is unlike a fax machine or e-mail account which is visible to any junk mailer who knows the telephone number or email address.
1 NETPAGE SYSTEM ARCHITECTURE
Each object model in the system is described using a Unified Modeling Language (UML) class diagram. A class diagram consists of a set of object classes connected by relationship:), and two kinds of relationships are of interest here: associations and generalizations. Ae association represents some kind of relationship between objects, ie. between instances of classes. A generalization relates actual classes, and can be understood in the following way. if a class ι$ thought of as the set of all objects of that class, and class
A is a geueralizaoon of class B, then B is simply a subset of A. The UML does not directly support second- order modelling - i.e. classes of classes.
Each class is drawn as a rectangle labelled with the name of the class. It contains a list of the attributes of the class, separated from the name by a horizontal line, and a list of the operations of the class, separated from the attribute list by a horizontal line. In the class diagrams which follow, however, operations are never modelled. An association u drawn as a line joining two classes, optionally labelled at either end with the multiplicity of the association. The default multiplicity is oαe. An asterisk (*) indicates a multiplicity of
"many", i.e. zero or more Each association is optionally labelled with its name, and is also optionally labelled at either end with the role of the corresponding class. An open diamond indicates an aggregation association ("is-part-of '), and is drawn at the aggregator end of the association line. A generalization relationship ("is-a") is drawn as a solid line joining two classes, with an arrow
(in the form of an open triangle) at the generalization end.
When a class diagram is broken up into multiple diagrams, any class which is duplicated is shown with a dashed outline in all but the main diagram which defines it It is shown with attributes only where it is defined. 1.1 NETPAGES
Netpages are the foundation on which a neipage network is built. They provide a paper-based user interface to published information and interactive services.
A netpage consists of a printed page (or other surface region) invisibly tagged with references to an online description of me page. The online page description is maintained persistently by a netpage page server. The page description describes the visible layout and content of the page, including text, graphics and images. It also describes the input elements on the page, including burtons, hyperlinks, and input fields. A netpage allows markings made with a netpage pen on its surface to be simultaneously captured and processed by the netpage system.
Multiple netpages can share the same page description. However, to allow input through otherwise identical pages to be distinguished, each netpage is assigned a unique page identifier. This page ID has sufficient precision to distinguish between a very large number of netpages. Each reference to the page description is encoded in a printed tag. The tag identifies the unique page on which it appears, and thereby indirectly ideoαfies the page description. The tig also identifies its own position on the page. Characteristics of the tags are described in more detail below
Tags are printed in infrared-absorptive ink on any substrate which is infrared-reflective, such as ordinary paper. Near-infrared wavelengths are invisible to the human eye but are easily sensed by a solid- state image sensor with an appropriate filter.
A tag is sensed by an area image censor in the netpage pen, and the tag data is transmitted to the neφage system via the nearest netpage printer. The pen is wireless and communicates with the netpage printer via a short-range radio link. Tags are sufficiently small and densely arranged that the pen can reliably image at least one tag even on a single click on the page. It is important that the pen recognize the page IO and position on every interaction with the page, since the interaction is stateless. Tags are error-correctably encoded to make them partially tolerant to surface damage.
The netpage page server m^nming. a unique page instance for each printed oetpage, allowing it to maintain a distinct set of user-supplied values for input fields in the page description for each printed netpage.
Tbe relationship between the page description, the page instance, and the printed netpage is shown in Figure 4. Tbe primed netpage may be part of a printed netpage document 45. The page instance is associated with both the αetpage printør which printed it and, if known, the netpage user who requested it.
As shown in Figure 4, one or more nctpages may also be associated with a physical object such as a product item, for example when printed onto the product item's label, packaging, or actual surface. 1.2 NETPAGE TAGS 1.2.1 Tag Data Content
In a preferred form, each tag identifies the region in which it appears, and tbe location of that tag within the region, A tag may also contain flags which relate to tbe region as a whole or to the tag. One or more flag bits may, for example, signal a tag sensing device to provide feedback indicative of a function associated with the immediate area of tbe tag, without the sensing device having to refer to a description of the region A neipage pen may, for example, illuminate an "active area" LED when in the zone of a hyperlink
As uill be more clearly explained below, in a prefeσed embodiment, each tag contains an easily recognized invariant structure which aids initial detection, and which assists in minimizing the effect of any warp induced by tbe surface or by the sensing process. The tags preferably tile the entire page, and are sufficiently small and densely arranged that the pen can reliably image at least one ug even on a single click on tbe page. It is important that the pen recognize the page ID and position on every interaction with the page, since the interaction ii stateless In a preferred embodiment, tbe region to which a rag refers coincide? with an entire page, and the region LO encoded in the tag is therefore synonymous with the page ID of the page on which the tag appears In other embodiments, tbe region to which a tag refers can be an arbitrary subregion of a page or other surface. For example, it can coincide with the zone of an interactive element, in which case the region ID can directly identify the interactive element In tbe preferred form, each tag contains 120 bits of information. The region (D iβ typically allocated up to 100 bite, the tag ID at least 16 bite, and the remaining bits are allocated to flags etc. Assuming a tag density of 64 per square inch, a 16-bit tag DD supporω a region βize of up to 1024 square inches. Larger regions can be mapped continuously without increasing the tag BD precision simply by using abutting regions and map3. The 100-bit region ID allows 2I<W (-1030 or a million trillion trillion) different regions to be uniquely identified. 1.2.2 Tag Data Encoding
In one embodiment, the (20 bits of tag data are redundantly encoded using a (15, 5) Reed- Solomon code. This yields 360 encoded bits consisting of 6 codewords of I S 4-bit symbols each. The (15, 5) code allows up to 5 symbol errors to be corrected per codeword, i.e. it is tolerant of a symbol error rate of up to 33% per codeword. Each 4-bit symbol is represented in a spatially coherent way in the tag, and the symbols of the six codewords are interleaved spatially within the tag- This ensures that a burst error (an error affecting multiple spatially adjacent bits) damages a minimum number of symbols overall and a minimum number of symbols in any one codeword, thus maximising the likelihood that the bum error can be fully corrected.
Any suitable error-correctine c°de code can ^e MS*d w P^6 of a (15, 5) Reed-Solomon code, for example: a Reed-Solomon code witfa more or lees redundancy, with the same or different symbol and codeword sizes; another block code; or a different kind of code, such as a convolution^ code (see, for example, Stephen B. Wicker, Error Conσol Systems far Digital Communication and Storage, Prentice-Hall 1995, the contents of which a herein incorporated by reference thereto).
In order to support "εingJe-click" interaction with a tagged region via a sensing device, the sensing device must be able to see at least one entire Ug in its field of view no matter where in the region or at what orientation it is positioned. The required diameter of the field of view of the sensing device is therefore a function of the size and spacing of the tags. 1.2.3 Tag Structure
Figure 5a snows a tag 4, in the form of tag 726 with four perspective targets 17. The tag 726 represents sixty 4-bit Reed-Solomon symbols 747, for a total of 240 bits. The tag represents each "one" bit by the presence of a mark 748, referred to as a macrodot, and each "zero" bit by the absence of the corresponding macTodot. Figure 5c shows a square tiling 728 of nine tags, containing all "one" bits for illustrative purposes. It will be noted that the perspective targets are designed to be shared between adjacent tags. Figure 5d shows a square tiling of 16 tags and a corresponding minimum field of view 193, which spans the diagonals of two tags.
Uslug a (15. 7) Reed-Solomon code, 112 bits of tag data are redundantly encoded to produce 240 encoded bits. The four codewords are interleaved spatially within the tag to maximize resilience to burst errors. Assuming β 16-bit tag ID as before, mis allows a region OD of up to 92 bite.
The data-bearing πiacrodoU 748 of the tag are designed to not overlap their neighbors, so that groups of tags cannot produce structures that resemble targets. This also saves ink. The perspective targets allow detection of roe tag, so further targets are not required.
Although the tag may contain an orientation feature to allow disambiguation of the four possible orientations of the tag relative to the sensor, the present Invention is concerned with embedding orientation data in the tag data. For example, the four codewords can be arranged so that each tag orientation (in a rotational sense) contains one codeword placed at that orientation, as shown in Figure 5a, where each symbol U labelled with the number of its codeword (M) and the position of the symbol within the codeword (A-O). Tag decoding then consists of decoding one codeword at each rotational orientation. Each codeword can eimer contain a single bit indicating whether it is the first codeword, or rwo bits indicating which codeword it is. The latter approach has che advantage that if, say, the data content of only one codeword is required, then at most two codewords need to be decoded to obtain the desired data. This may be the case if the region ID is not expected to change within a stroke and is thus only decoded at the start of a stroke. Within a stroke only the codeword containing the tag ID is then desired. Furthermore, since the rotation of the sensing device changes εlowly and predictably within a stroke, only one codeword typically needs to be decoded per frame.
It is possible to dispense with perspective targets altogether and instead rely on the data representation being self-registering. In this case each bit value (or tnuld-bit value) iε typically represented by an explicit glyph, Le. no bit value is represented by the absence of a glyph. This ensures that the data grid is we U -populated, and thus allows the grid to be reliably identified and its perspective distortion detected and subsequently corrected during data sampling. To allow tag boundaries to be detected, each tag data must contain a marker pattern, and these must be redundantly encoded to allow reliable detection The overhead of such marker patterns is βimilar to the overhead of explicit perspective targets. Various such schemes are described in the present applicants' co-pending PCT application PCT/ AU01/01274 filed 11 October 2001.
The arrangement 728 of Figure 5c shows that the square tag 726 can be used to fully tile or lesβelate, i.e. without gaps or overlap, a plane of arbitrary size.
Although in preferred embodiments the tagging schemes described herein encode a single data bit using the presence or absence of a single undifferentiated macrodot, they can also uβe sets of differentiated glyphs to represent single-bit or multi-bit values, such as the sets of glyphs illustrated in the present applicants' co-pending PCT application PCT/AU01/01274 filed 11 October 2001 1.3 THE NETPAGE NETWORK
In a preferred embodiment, a netpage network consists of a distributed set of netpage page servers 10, netpage registration servers U, netpage ID servers 12, netpage application servers 13, netpage publication servers 14, Web terminals 75, ncipage primers 601 , and relay devices 44 connected via a network 19 such as the Internet, as shown in Figure 3.
The netpage registration server 11 is a server which records relationships between users, pens, printers, applications and publications, and thereby authorizes various network activities. It authenticates users and acts as β signing proxy on behalf of au-beocicated users in application transactions. It also provides handwriting recognition services. As described above, a netpage page server 10 maintains persistent information about page descriptions and page instances. The netpage network includes any number of page servers, each handling a subset of page instances. Since a page server also maintains user input values for each page instance, clients such as netpage printers send netpage input directly to the appropriate page server. The page server interprets any such input relative to the descnpbon of the corresponding page. A netpage DD server 12 allocates document IDs 51 on demand, and provides load-balaocing of page servers via its ID allocation scheme.
A netpage printer uses the Internet Distributed Name System (DNS), or similar, to resolve a netpage page (D 50 into the network address of the 'netpage page server handling the corresponding page instance. A netpage application server 13 is a server which hosts interactive netpage applications. A netpage publication server 14 is an application server which publishes netpage documents to netpage printers. Netpage servers can be hosted on a variety of network server platforms from manufacturers such as IBM, Hewlett-Packard, and Sun. Multiple netpage servers can run concurrently on a single host, and a single server can be distributed over a number of hosts. Some or all of the functionality provided by netpage servers, and in particular the functionality provided by the [D server and the page server, can also be provided directly in a netpage appliance such a9 a netpage primer, in a computer workstation, or on a local network.
1.4 THE NETPAGE PRINTER
The netpage printer 601 is an appliance which ia registered with the netpage system and prints netpage documents on demand and via subscription. Each printer has a unique printer ID 62, and iε connected to the netpage network via a network such as the Internet, ideally via a broadband connection.
Apart from identity and security settings in non-volatile memory, the netpage printer contains no persistent storage. As far as a user is concerned, "the network is the computer". Netpages function interactively across space and time with toe help of the distributed neipage page servers 10, independently of particular netpage printers. The netpage printer receives subscribed netpagβ documents from netpage publication servers 14.
Each document is distributed in two parts: the page layouts, and the actual text and image objects which populate the pages. Because of personalization, page layouts are typically specific to a particular subscriber and so are pointcast to the subscriber's printer via the appropriate page server. Text and image objects, on the other hand, are typically shared with other subscribers, and so are multicast to all subscribers' printers and the appropriate page servers.
The oetpage publication server optimizes the segmentation of document content into pointcaats and muHicasts. After receiving the pointcast of a document's page layouts, the printer knows which multicast*, if any, to listen to.
Once the printer has received the complete page layouts and objects that define the document to be primed, it can print the document.
The printer rasterizes and prims odd and even pages simultaneously oo both sides of the sheet- It contains duplexed print engine controllers 760 and print engines utilizing Memjet™ printheads 350 for this purpose.
The printing process consists of two decoupled stages: rasterization of page descriptions, and expaωioo and printing of page images The raster image processor (IUP) consists of one or more standard
DSPs 757 running in parallel. The duplexed print engine controllers consist of custom processors which expand, dither and print page images in real time, synchronized with the operation of the printheads in the print engines.
Printers not enabled for IR printing have the option to pnnt tags using IR-absorpnve black ink, although this restricts tags to otherwise empty areas of the page. Although such pages have more limited functionality than lR-printed pages, they are still classed as netpages.
A normal netpage printer prints netpage. on sheets of paper. More specialised netpage printers may print onto more specialised surfaced, auch as globes. Each printer supports at least one surface type, and supports at least one tag tiling scheme, and hence tag map, for each surface type. The tag map 8 I l which describes the tag tiling scheme actually used to print a document becomes associated with that document so that the document's tags can be correctly interpreted. Figure 2 shows the netpage printer class diagram, reflecting printer-related information maintained by a registration server 1 1 on the netpagβ network. 1.5 THE NETPAGE PEN
The active sensing device of the netpage system is typically a pen 101 , which, using its embedded controller 134, is able to capture and decode OR. position tags from a page via an image sensor The image sensor is a solid-state device provided with an appropriate filter to permit sensing at only near-infrared wavelengths. As described in more detail below, the system is able to sense when the nib is in contact with the surface, and the pen is able to sense tags at a sufficient rate to capture human handwriting (i.e. at 200 dpi or greater and 100 Hz or faster). Information captured by the pen is encrypted and wireleasly transmitted to the printer (or base station), the printer or base station interpreting me data with respect to the (known) page structure.
The preferred embodiment of the netpage pen operates both as a normal marking ink pen and as a non-marking stylus. The marking aspect, however, is not necessary for using the netpage system as a browsing system, such as when it is used as an Internet interface. Each netpage pen is registered with the netpage system and has a unique pen ID 61. Figure 14 shows the netpage pen class diagram, reflecting pen- related information maintained by a registration server 1 1 on the netpage network.
When either nib is in contact with a netpage, the pen determines its position and orientation relative to the page. The nib is attached to a force sensor, and the force on me nib is interpreted relative to a threshold to indicate whether the pen is "up" or "down". This allows a interactive element on the page to be 'clicked' by pressing with the pen nib, in order to request, say, information from a network. Furthermore, the force ώ captured as a continuous value to allow, say, the full dynamics of a signature to be verified.
The pen determines the position and orientation of its nib on the netpage by imaging, in the infrared spectrum, an area 193 of the page in the vicinity of the nib. It decodes me nearest tag and computes the position of the nib relative to the tag from the observed perspective distortion on the imaged tag and the known geometry of the pen optics. Although the position resolution of tho tag may be low, because the tag density on the page is inversely proportional to the tag size, the adjusted position resolution is quite high, exceeding the minimum resolution required for accurate handwriting recognition.
Pen actions relative to a netpage are captured as a series of strokes. A stroke consists of a sequence of time-stamped pen positions on the page, initiated by a pen-down event and completed by the subsequent pen-up event. A stroke is also tagged with the page ID 50 of the netpage whenever the page ID changes, which, under normal circumstances, is at the commencement of the stroke.
Each netpage pen has a current selection 826 associated with it, allowing the user to perform copy and paste operations etc. The selection is timestamped to allow the system to discard it after a defined tune period. The current selection describes a region of a page instance It consists of the most recent digital ink stroke captured through the pen relative to the background area of the page. It is interpreted in an application- specific manner once it is submitted to an application via a selection hyperlink acovanon
Each pen has a current nib 824. This is the nib last notified by the pen to the system. In the case of the default netpage pen described above, either the marking black ink cub or the non-marking stylus nib is current. Each pen also has a current nib style 823. This is the nib style last associated with the pen by an application, e.g. in response to the user selecting a color from a palette. The default nib style is the nib style associated with the current nib. Strokes captured through a pen are tagged with the current nib style. When the strokes are subsequently reproduced, they are reproduced in the nib style with which they are tagged.
Whenever the pen is within range of a printer with which it can communicate, the pen slowly flashes its "online" LEO- When the pen fails to decode a stroke relative to tha page, it momentarily activates its "error" LED. When the pan succeeds in decoding a stroke relative to the page, it momentarily activates its "ok" LED.
A sequence of captured strokes i9 referred to as digital ink. Digital ink forms the basis for the digital exchange of drawings and handwriting, for online recognition of handwriting, and for online verification of signatures. The pen is wireless and transmits digital ink to the netpage printer via a short-range radio link.
Tbe transmitted digital ink is encrypted for privacy and security and packetized lor efficient transmission, but is always flushed on a pen-up event to ensure timely handling in the printer.
When the pen is out-of-range of a printer it buffers digital ink in internal memory, which has a capacity of over ten minutes of continuous handwriting. When the pen is once again within range of a printer, it transfers any buffered digital ink.
A pen can be registered with any number of printers, but because all state data resides in netpages both oo paper and on the network, it is largely immaterial which printer a pen is communicating with ai any particular tune.
A preferred embodiment of the pen ie described in greater detail below, with reference to Figures 6 to 8.
1.6 NETPAGE INTERACTION
The netpage printer 601 receives data rotating to a stroke from the pen 101 when the pen w used to interact with a netpage 1. The coded data 3 of the tags 4 is read by the pen when it it used to execute a movement, such as a stroke. The data allows the identity of the particular page and associated interactive element to be determined and an indication of the relative positioning of the pen relative to the page to be obtained. The indicating data is transmitted to the printer, where it resolves, via the DNS, the page ID 50 of the stroke into the network address of the oetpage page server 10 which maintains the corresponding page instance 830. It then transmits the stroke to the page server. If the page was recently identified in aα earlier stroke, then tbc printer may already have the address of the relevant page server in its cache. Each netpage consists of a compact page layout maintained persistently by β netpage page server (see below). The page layout refers to objects such as imaged, fonts and pieces of text, typically stored elsewhere on the netpage network.
When the page server receives the stroke from the pea, it retrieves the page description to which the stroke applied, and determines which element of the page description the stroke intersects. It is then able to interpret the stroke in the context of the type of the relevant element.
A "click" is a stroke where the distance and time between the pen down position and the subsequent pen up position are both less than some small maximum. An object which is activated by a click typically requires a click to be activated, and accordingly, a longer stroke is ignored. The failure of a pen action, such as a "sloppy" click, to register is indicated by the lack of response from the pen's "ok" LED. There are two kinds of input elements in a netpage page description hyperlinks end form fields.
Input through a form field can also trigger the activation of an associated hyperlink. 2 NETPAGE PEN DESCRIPTION
2.1 PEN MECHANICS
Referring to Figures 6 and 7, the pen, generally designated by reference numeral 10l , includes a housing 102 in the form of a plastics moulding having walls 103 defining an interior space 104 for mounting the pen components. The pen top 105 is Jn operation rotatably mounted at one end 106 of the bo serai-transparent cover 107 is secured to the opposite end 108 of the bousing 102. The cover 1 moulded plastics, and is formed from semi-transparent material in order to enable the user to vi of the LED mounted within the bousing 102. The cover 107 includes a F^Π pan 109 which substantially surrounds the end 108 of the bousing 102 and a projecting portion 110 which projects back from the main part 109 and fits within a corresponding slot 111 formed in the walls 103 of the housing 102. A radio antenna 112 is mounted behind the projecting portion 110, within the housing 102. Screw threads 1 13 surrounding an aperture 113A OD the cover 107 are arranged to receive a metal end piece 1 14, including corresponding screw threads 1 15. The metal end piece 114 is removable to enable ink cartridge replacement.
Also mouoted within the cover 107 U a tri-color stacua LED 1 16 on a Qβx PCB 1 17. The antenna 112 is also mounted on the flex PCB 117. The status LED 1 16 1. mounted at the top of the pen 101 for good all-around visibility.
The pen can operate both as a normal marking ink pen and as a non-marking stylus. An ink pen cartridge 118 with nib 119 and a stylus 120 with stylus nib 121 are mounted side by side within the housing 102. Either the ink cartridge nib 119 or the stylus nib 121 can be brought forward through open end 122 of the metal end piece 1 14, by rotation of the pen top 105. Respective slider blocks 123 and 124 are mounted to the ink cartridge 118 and stylus 120, respectively. A rotatable cam barrel 125 is secured to the pen top 105 in operation and arranged to rotate therewith. The cam barrel 125 includes a cam 126 in the form of a slot within the walls 181 of the cam barrel Cam followers 127 and 128 projecting from slider blocks 123 and 124 fit witiun the cam 9lot 126. On rotation of the cam barrel 125, the slider blocks 123 or 124 move relative to each other to project either the pen nib 1 19 or stylus nib 121 out through the hole 122 In the metal end piece 1 14. The pen 101 has three states of operation. By turning the top 105 through 90β steps, the three states are:
• stylus 120 nib 121 out
• ink cartridge 1XΘ nib 119 out, and
• neither ink cartridge HS nib 119 out nor stylus 120 nib 121 out
A second flex PCB 129. is mounted on an electronics chassis 130 which sits within the housing 102. The second flex PCB 129 mounts an infrared LED 131 for providing infrared radiation for projection onto the βuriace. An image sensor 132 is provided mounted on the second flex PCB 129 for receiving reflected radiation from the surface. The second flex PCB 129 also mounts a radio frequency chip 133, which includes an RF transmitter and RF receiver, and a controller chip 134 for controlling operation of the pen 101. An optics block 135 (formed from moulded clear plasties) sits within the cover 107 and projects an infrared beam onto the surface and receives images onto the image sensor 132. Power supply wires 136 connect the components on the second flex PCB 129 to battery contacts 137 which are mounted within the cam barrel 125. A terminal 138 connects to the battery contacts 137 and the cam barrel 125. A three volt rechargeable battery 139 sits within the cam barrel 12S in contact with the battery contacts. An induction charging coil 140 is mounted about the βecond flex PCB 129 to enable recharging of the battery 139 via induction. The second flex PCB 129 also mounts an infrared LED 143 and infrared photodiode 144 for detecting displacement in tte cam barrel 125 when either (be stylus 120 or the ink cartridge 118 iβ used for writing, in order to enable a determination of the force being applied to the surface by the pen nib 119 or srylus nib 121. The IR pbotodiode 144 detects light from the IR LED 143 via reflectors (not shown) mounted on the slider blocks 123 and 124.
Rubber grip pads 141 and 142 are provided towards the end 108 of the housing 102 to assist gripping the pen 101 , and top 105 also includes a clip 142 for clipping the pen 101 to a pocket. 3.2 PEN CONTROLLER
The pen 101 is arranged to determine the position of its nib (stylus nib 121 or ink cartridge nib 119) by imaging, in the infrared spectrum, an area of the surface in the vicinity of the nib. It records the location data from the nearest location tag, and is arranged to calculate the distance of the rub 121 or 1 19 from the location tab utilising optics 135 and controller chip 134. The controller chip 134 calculates the orieαtαxion of the pen and the nib-to-tag distance from the perspective distortion observed on the imaged tag
Utilising the RF chip 133 and anteαna 1 12 the pen 101 can transmit the digital ink data (which is encrypted for security and packaged for efficient transmission) to the computing system.
When the pen is in range of a receiver, the digital ink data is transmitted as it is formed When the pen 101 moves out of range, digital ink data is buffered wiihin the pen 101 (the pen 101 circuitry includes a buffer arranged to store digital ink data for approximately 12 minutes of the pen motion on the surface) and can be transmitted later. The controller chip 134 is mounted on the second flex PCB 129 in the pen 101. Figure 6 is a block diagram illustrating in more detail the architecture of the controller chip 134. Figure 8 also shows representations of the RF chip 133, the image sensor 132, the tri-color status LED 116, the IR illumination T FT> 131, the IR force sensor LED 143, and the force sensor photodiode 144.
The pen controller chip 134 includes a controlling processor 145. Bus 146 enables the exchange of data between components of the controller chip 134. Flash memory 147 and a 512 KB DRAJVt 148 are also included. Aa analog-to-digital converter 149 is arranged to convert the analog signal from the force seneor photodiode 144 to a digital signal.
An image sensor interface 152 interfaces with the image sensor 132. A transceiver controller 153 and base band circuit 154 are also included to interface with the RF chip 133 which includeε an RF circuit 155 and RF resonators and inductors 156 connected to (be antenna 112.
The controlling processor 145 captures and decodes location data from tags from the surface via the image sensor 132, monitors the force sensor photodiode 144, controls the LEDs 1 16, 131 and 143, and handles short-range radio communication via the radio transceiver 153. It is a medium-performance (-40MHz) general-purpose RISC processor. The processor 145, digital transceiver components (transceiver controller 153 and baseband cirouit 154), image sensor interface 152, flash memory 147 and 512KB DRAM 14S are integrated in a single controller ASIC. Analog RF components (RF circuit 155 and RF resonators and inductors 1S6) are provided in the separate RF chip.
Tba image sensor is β CCD or CMOS image sensor. Depending oo tagging scheme, it has a size ranging from about 100x100 pixels to 200x200 pixels. Many miniature CMOS image sensors are commercially available, including the National Semiconductor LM9630. The controller ASIC 134 enters a quiescent smte after a period of inactivity when the pen 101 is not in contact with a surface. Ic incorporates a dedicated circuit 150 which monitors the force sensor photodiode 144 and wakes up the controller 134 via the power manager 151 on a pen-down event.
The radio transceiver communicates in the unlicensed 900MHz band normally used by cordless telephones, or alternatively in the unlicensed 2.4OHz industrial, scientific and medical (ISM) band, and uβeβ frequency hopping and collision detection to provide interference-free communication.
ID an alternative embodiment, the pen incorporateβ an Infrared Data Association (IrDA) interface for short-range communication with a base station or notpage printer.
In a further embodiment, the pen 101 includes a pair of orthogonal βccelerometers mounted in the normal plane of the pen 101 axis. The accelerometerβ 190 are shown in Figures 7 and 8 in ghost outline.
The provision of the accelerometera enables this embodiment of the pen 101 to εenεe motion without reference to surface location tags, allowing the location tags to be sampled at a lower rate. Each location tag ID can then identify an object of interest rather than a position on the surface. For example, if the object is a user interface input element (e.g. a command button), then the tag ID of each location tag within the area of the input element can directly identify the input element.
The acceleration measured by the accelerometers Ln each of the x and y directions is integrated with respect to time to produce an instantaneous velocity and position.
Since the starting position of the stroke is not known, only relative positions within a 9troke are calculated. Although position integration accumulates errors in the sensed acceleration, aecelerometers typically have high resolution, and the time duration of a 9troke, over which errors accumulate, is short.
3 NETPAGE PRINTER DESCRIPTION
3.1 PRINTER MECHANICS
The vertically-mounted netpage wallpnnter 601 is shown fully assembled in Figure 9. It prints netpagβs on Letter/A4 sized media using duplexed 8Va" Memjet™ print engines 602 and 603, as shown in Figures 10 and 1Oe. It uses a straight paper path with the paper 604 passing through the duplexed print engines 602 and 603 which print both sides of a sheet simultaneously, in full color and with full bleed.
An integral binding assembly 605 applies a stπp of glue along one edge of each printed sheet, allowing it to adhere to the previous sheet when pressed against it. This creates a final bound document 618 which can range in thickness from one sheet to several hundred sheets. The replaceable ink cartridge 627, shown in Figure 12 coupled with the duplexed print engines, has bladders or chambers for storing fixative, adhesive, and cyan, magenta, yellow, black and infrared inks.
The cartridge al9o contains a micro air filter in a base molding. The micro air filter interfaces with an air pump 638 inside the printer via a hose 639. This provides filtered air to the prlntheads to prevent ingrcis of micro particles into tbe Memjet™ printheads 350 which might otherwise clog ύV printhead nozzles. By incorporating the air filter witbm the cartridge, the operational life of the filter is effectively linked to the life of tbe cartridge. The ink cartridge is a fully recyclable product with a capacity for printing and gluing 3000 pages (1500 sheets).
Referring to Figure 10, the motorized media pick-up roller assembly 626 pushes the top sheet directly from the media tray past a paper sensor on the first print engine 602 into the duplexed Memjet™ prLnthead assembly. The two Memjet™ print engines 602 and 603 are mounted in on opposing in-line sequential configuration along me straight paper path The paper 604 is drawn into the first print engine 602 by integral, powered pick-up rollers 626. The position and size of the paper 604 is sensed and ftill bleed printing commences. Fixative is printed simultaneously to aid drying in the shortest possible tinv
The paper exits the first Memjet™ print engine 602 through a set of powered exit spike wheels (aligned along the straight paper path), which act against a rubberized roller. These spike wheels contact the 'wet' printed surface and continue to feed the sheet 604 into the second Memjet™ print engine 603.
Referring to Figures 10 and 10a, the paper 604 peases from the duplexed print engines 602 and 603 into the binder assembly 605. The printed page passes berween a powered spike wheel axle 670 with a fibrous εupport roller and another movable axle with spike wheels and a momentary action glue wheel. Too movable axle/glue assembly 673 is mounted to a metal support bracket and it ύ transported forward lo interface with the powered axle 670 via gears by action of a camshaft. A separate motor powers this camshaft.
The glue wheel assembly 673 consists of a partially hotlow axle 679 with a rotating coupling for the glue supply hose 641 from the ink cartridge 627. This axle 679 connects to a glue wheel, which absorbs adhesive by capillary action through radial holes. A molded housing 692 surrounds the glue wheel, with an opening at the from. Pivoting side moldings and sprung outer doors are attached to the metal bracket and hinge out sideways when the rest of the assembly 673 is thrust forward. This action exposes the glue wheel through the front of the molded housing 682. Tension springs close toe assembly and effectively cap the glue wheel during periods of inactivity. As the sheet 604 passes into the glue wheel assembly 673, adhesive is applied to one vertical edge on the front side (apart from the first sheet of a document) as it is transported down into the binding assembly 605.
4 PRODUCT TAGGING Automatic identification refers to the use of technologies such as bar codes, magnetic stripe cards, smartcards, and RF transponders, to (sβ-cu-)autorαatically identify objects to data processing systems without manual keying.
For the purposes of automatic identification, a product item is commonly identified by a 12 -digit
Universal Product Code (UPC), encoded mactune-readably in the form of a printed bar code. The most common UPC numbering system incorporates a 5-digit manufacturer number and a 5-digic item number.
Because of its limited precision, a UPC is used to identify a class of product rather than aα individual product item. The Uniform Code Council and EAN International define and administer the UPC and related codes as subsets of the 14-digit Global Trade Item Number (GTIN).
Within supply chain management, there is considerable interest in expanding or replacing the UPC scheme to allow individual product items to be uniquely identified and thereby tracked. Individual item tagging can reduce '•shrinkage" due to lost, stolen or spoiled goods, improve the efficiency of demand-driven manufacturing and supply, facilitate the profiling of product usage, and improve the customer experience.
There are two main contenders for individual item tagging: optical tags in the form of so-called two-dimensional bar codes, and radio frequency identification (RFID) tags. For a detailed descriprion of RFID tags, refer to Klaus Finkenzeller, RFID Handbook, John Wiley & Son (1999), the contents of which are herein incorporated by cross-reference. Optical tags have me advantage of being inexpensive, but require optical line-of-sjght &r reading. RFID tags have the advantage of supporting onmidirection-tl reading, but are comparatively expensive. The presence of metal or liquid can seriously interfere with RFID tag performance, undermining the omnidirectional reading advantage. Passive (reader-powered) RFID tags are projected to be priced at IO cents each io multi-million quantities by the eod of 2003, and at 5 cents each soon thereafter, but this still falls shoπ of the sub-one-cent industry target for low-price items such as grocery. The read-only nature of most optical tags has also been cited as a disadvantage, since status changes cannot be written to a tag as an item progresses through the supply chain. However, this disadvantage is mitigated by the fact that a read-only tag can refer to information maintained dynamically on a network
The Massachusetts Institute of Technology (MlT) Aιπo-ID Center has developed a standard for a 96-bit Electronic Product Code (EPC), coupled with an Internet-based Object Name Service (ONS) and a Product Markup Language (PML). Once an EPC is scanned or otherwise obtained, it is used to look up, possibly via the ONS, matching product information poπably encoded in PML. The EPC consists of an 8-bit header, a 28-bit EPC manager, a 24-bit object class, and a 36-bit serial number. For a detailed description of the EPC, refer to Brock, D.L., The Electronic Product Code (EPC), M]T Auto-ID Center (January 2001), the contents of which are herein incorporated by cross-reference. The Auto-ID Center has defined a mapping of the GTIK onto the EPC to demonstrate compatibility berween the EPC and current practices Brock, D L , Integrating the Electronic Product Code (EPC) and the Global Trade Item Number (GTIN), MIT Auto-ID Center (November 2001), the contents of which are herein incorporated by cross-reference. The EPC is administered by EPCglobal, an EAN-UCC joint venture. EPCs are technology-neutral and oan be encoded and carried in many forms. The Auto-ID Center strongly advocates the use of low-cost passive RFID tags to carry EPCs, and lias defined a 64-bit version of the EPC to allow the cost of RFID tags to be minimized ut the ahoπ term. For detailed description of low- cost RFID teg characteristic*, refer to Sarma, S., Towards the Sc Tag, MΪT Auto-ID Center (November 2001), the contents of which are herein incorporated by cross-reference. For a description of a commerciatiy- available low-cost passive RFID tag, refer to 915 MHz RFID Tag, Alien Technology (2002), the contents of which are herein incorporated by cross-reference. For detailed description of the 64-bit EPC, refer to Brock, D.L., The Compact Electronic Product Code, MTT Auto-ID Center (November 2001), the contents of which are herein incorporated by cross-reference.
EPCs are intended not just for unique item-level tagging and tracking, but also for case-level and pallet-level tagging, and for tagging of other logistic units of shipping and transportation such as containers and trucks. The distributed PML database records dynamic relationships between items and hjgocr-levd containers In the packaging, shipping and transportation hierarchy.
4.1 OMNITAGGING IN THE SUPPLY CHAIN Using an invisible (e.g. infrared) tagging scheme to uniquely identify a product item has the significant advantage that it allows the entire surface of a product to be tagged, or a significant portion thereof; without impinging on the graphic design of the product's packaging or labelling. If the entire product surface is tagged, then the orientation of the product doesn't affect its ability to be scanned, i.e. a significant part of the line-of-sight disadvantage of a visible bar code is eliminated. Furthermore, since the tags are small and massively replicated, label damage no longer prevents scanning. Oαraitegging, then, consists of covering a large proportion of the surface of a product item with optically-readable invisible tags. Each onmitag uniquely identifies the product item on which it appears. The omaitag may directly encode the product code (e.g. EPC) of the item, or may encode a surrogate IO which in turn identifies the product code via a database lookup. Each ornnitag also optionally identifies its own position on the surface of the product item, to provide the downstream consumer benefits of netpage interactivity described earlier.
Omniugs are applied during product manufacture and/or packaging using digital printers. These may be add-on infrared printers which print the omrutags after the text and graphics have been printed by other means, or integrated color and infrared printers which print the omnitags, text and graphics simultaneously. Digitally-printed text and graphics may include everything on the label or packaging, or may consist only of the variable portions, with other portions still printed by other means. 4.2 OMNITAGGING
As shown in Figure 13, a product's unique item ID 2 I S may be seen as a special kind of unique object ID 210. The Electronic Product Code (EPC) 220 is one emerging standard for an item DD. An item ID typically consists of a product ID 214 and a serial number 213. The product QD identifies a class of product, while tbe serial number identifies a particular instance of that class, i.e. an individual product item. The product ID in turn typically consists of a manufacturer number 2) 1 and a product class number 212. The best-known product ID is the EAKUCC Universal Product Code (UPC) 221 and its variants.
As shown in Figure 14, an omnitag 202 encodes a page ID (or region ID) SO and a two- dimensional (2D) position 66. The region ID identifies me surface region containing the tag, and the position identifies tbe tag's position within the two-dimensional region. Since the surface in question is the surface of a physical product item 201, it iε useful to define a one-to-one mapping between the region ID and the unique object ID 210, and more specifically the item ID 215, of the product item. Note, however, that the mapping can be many-to-one without compromising the utility of me omnitag. For example, each panel of a product item's packaging could have a different region ID S0. Conversely, the omniug may directly encode the item
[D, in which case the region ID contains the item ID, suitably prefixed to decouple item ID allocation from general netpage region ID allocation. Note that the region ID uniquely distinguishes the corresponding surface region from all other surface regions identified within tbe global netpage system.
The item DD 215 is preferably the EPC 220 proposed by the Auto-ID Center, since this provides direct compatibility between omnitags and EPC-carrying RFID tags.
In Figure 14 the position 66 is shown as optional. This id to indicate that much of the utility of tbe omrutag in the supply chain derives from the region ED 50, and the position may be omitted if not desired for a particular product.
For interoperability with the netpage system, an omnitag 202 is a netpage tag 4, i e. it has me logical structure, physical layout and semantics of a netpage tag.
When a netpage sensing device such as the netpage pen 101 images and decodes an omnitag, it uses the posiάoo and orientation of the tag in its field of view end combines this with the position encoded in the tag to compute its own position relative to the lag. As tbe sensing device is moved relative to a
Hyperlabelled surface region, it is thereby able to track its own motion relative to tbβ region and generate a set of timestamped position samples representative of its time-varying path. When the sensing device is a pen, then the path consists of a sequence of strokes, with each stroke starting when the pen makes contact with the surface, and ending when the pen breaks contact with the surface.
When a stroke is forwarded to the page server 10 responsible for the region ID, the server retrieves a description of the region keyed by region ID, and interprets the stroke in relation to the description. For example, if tbe description includes a hyperlink and the stroke intersects the zone of the hyperlink, then the server may interpret the stroke as a designation of tbe hyperlink and activate the hyperlink
4.3 OMNITAG PRINTING
An omnitag primer is a digital printer which prints ommtag- onto the label, packaging or actual surface of a product before, during or after product manufacture and/or assembly. It is a special case of a nerpage printer 601. It is capable of printing a continuous pattern of omnitags onto a surface, typically using a near-iofrared-absoφtive ink. In high-speed environments, the printer includes hardware which accelerates tag rendering. This typically includes real-tune Reed-Solomoα encoding of variable tag data such as tag position, and real-time template-based rendering of the actual tag pattern at the dot resolution of tbe pnntbead. The printer may be an add-on infrared printer which prints the omnitags after text and graphics have been printed by other means, or an integrated color and infrared printer which prints the omnitags, text and graphics simultaneously Digitally-printed text and graphics may include everything on the label or packaging, or may consist only of tbe variable portions, with other portions still printed by other means. Thus an omnitag printer with an infrared and black printing capability can displace an existing digital printer used for variable data printing, such as a conventional thermal transfer or inkjet printer.
For the purposes of tbe following discussion, any reference to printing onto an item label is intended to include printing onto (he item packaging in general, or directly onto the item surface. Furthermore, any reference to an item BD 215 i6 intended to include a region ID S0 (or collection of per-panel ' region ids), or a component thereof. The printer is typically controlled by a host computer, which supplies the printer with fixed and/or variable text and graphics as well as item ids for inclusion in the omnitags. The host may provide real-time control over the printer, whereby it provides the printer with data in real time as printing proceeds. As an optimisation, the host may provide the printer with fixed data before printing begins, and only provide variable data in real ctcuc. Tbe printer may also be capable of generating per-itera variable data based on parameters provided by the host For example, the host tnay provide the printer with a base item ID prior to printing, and the printer may simply increment tho base item UD to generate successive item ids. Alternatively, memory in tbe ink cartridge or other storage medium inserted into the printer may provide a source of unique item ids, in which case the printer reports the assignment of items ids to tbe host computer for recording by the host. Alternatively stiU, the printer may be capable of reading a pre-existing item ID from the label onto which tbe omnitags are being printed, aεsuming tbe unique ID has been applied in some form to tbe label during a previous manufacturing step. For example, the item ID may already be present iα the form of a visible 2D bar code, or encoded in an RFID tag. In the former case the printer can include an optical bar code scanner. In tbe latter case it can include an RFtO reader. The printer may also be capable of rendering the item ID in other forms. For example, it may be capable of printing the item ID in the form of a 2D bar code, or of printing the product ED component of the item ID in the form of a ID bar code, or of writing the item ID to a writable or write-once RFID tag.
4.4 OMNITAG SCANNING Item information typically flows to the product server in response to situated scan events, e.g. when an item is scanned into inventory on delivery; when the item ύ placed oo a retail shelf; and when the item is scanned at point of sale. Both fixed and hand-held scanners may be used to scan omnitagged product items, using both laser-based 2D scanning and 2D image-sensor-based scanning, using similar or the same techniques 89 employed in the netpage pen. As shown in Figure 16, both a fixed scanner 254 and a hand-held scanner 252 communicate scan data to the product server 251. The product server may in mm communicate product item event data to a peer product server (not shown), or to a product application server 2S0, which may implement sharing of data with related product servers. For example, stock movements within a retail store may be recorded locally on the retail store's product server, but the manufacturer's product server may be notified once a product item Ls sold.
4.5 OMNITAG-BASED NETPAGE INTERACTIONS
A product item whose labelling, packaging or actual surface has boon omnitaggcd provides the same level of interactivity as any other netpage.
There is a strong case to be made for netpage-compatible product tagging. Netpage rums any printed surface into a finely differentiated graphical user interface akin to a Web page, and there are many applications which map nicely onto the surface of a product. These applications include obtaining product information of various kinds (nutritional information; cooking instructions; recipes; related products; u≤β-by dates; servicing instructions; recall notices); playing games; entering competitions; managing ownership (registration; query, such as in the case of stolen goods; transfer); providing product feedback; messaging; and Indirect device control. If, on the other hand, the product tagging is undifferentiated, such as in the cose of an undifferentiated 2D barcode or RFID-carried item ID, then the burden of information navigation is transferred to the information delivery device, which may significantly increase me complexity of the user experience or the required sophistication of the delivery device user interface.
The invention will now be described with reference to the following examples. However, it will of course be appreciated that this invention may be embodied in many other forms without departing from the scope of the invention, as defined in the accompanying claims.
Examples
Example 1 • Preparation of hydroxygallium naphthalocyaninetetrasulfonic acid 4
Figure imgf000044_0001
Scheme 1
(i) GalliumOff) chloride (5 70 g; 0.032 mol) was dissolved in anhydrous toluene (68 mL) under β slow stream of nitrogen and then the resulting solution was cooled in ice/water. Sodium methoxide (25% in methanol; 23.4 mL) was added slowly with stimng causing a thick white precipitate to form Upon completion of the addition, the mixture was stirred at room temperature for 1 h and then naphlnakne-2,3- dicarbonitrile (22 S g; 0.128 mol) was added pornoowvse, followed by triethylene glycol monomethyl ether (65 mL). The thick slurry was distilled for 2 h to remove the methanol and toluene. Once the toluene had distilled off, the reaction mixture became homogeneous and less viscous and stirred readily. Heating was continued for 3 h at 190 °C (internal). The brown/black reaction mixture was cooled to 60 °C, diluted with chloroform (I S0 mL), and filtered under gravity through a sintered glass runnel The solid residue was washed with more chloroform (50 mL) and then a further portion (50 mL) with suction under reduced preasure. The resulting dark green solid was then sequentially washed under reduced pressure with acetone (2 x 50 mL), DMF (2 x 50 DiL), water (2 x 50 mL), acetone (2 x 50 mL), and diethyl ether (2 x 50 mL). The moist solid was air-dried to a dry powder and then healed under high vacuum at ca 100 *C for 1 h to complete the drying process. Naphthafocyauinatogallium mechoxytriethyleneoxide 3 was obtained as β fine dark green powder (23.14 g; 80%), λ^ (NMP) 770 nm.
(ii) Napbtnalocyaninatogaltium methoxytriethyleneoxide 3 (9.38 g; 0.010 mol) was treated with 30% oleum (47 mL) by slow addition via a dropping runnel while cooling in an ice/water bath under a nitrogen atmosphere. Upon completion of the addition, the reaction mixture was transferred to a preheated water bath at 55 °C and stirred at this temperature for 2 b during which time the mixture became a homogeneous viscous dark blue solution. The stirred reaction mixture was cooled in an ice/water bath and then 2-propanol (40 mL) was added slowly via a dropping funnel. This mixture was then poured into 2-propaαol (100 mL) using more 2-propanol (160 mL) to wash out the residues from the reaction flaak. Diethyl ether (100 mL) *ai then added to the mixture which was then transferred to a sintered glass funnel and filtered under gravity affording a moist dark brown solid and a yellow/brown filtrate. The solid was washed sequentially with ether (50 mL), acetone/ether (1 : 1, 100 mL), and ether (100 mL) with suction under reduced pressure. The resulting solid (13.4 g) after drying under high vacuum was then stirred in ethanol/ether (1 :3, 100 raL) for 3 days and then filtered and dried to give the tetrasulfonic acid 4 as a fine red/brown solid (12.2 g; 105% of theoretical yield; 90% purity according to potentiometric titration). 1H NMR (Jg-DMSO) δ 7.97, 8.00 (4H, dd, J 7.5 - Λ. " 7-2 Hz, H7); 8.49 (4H. dd. J,,7 - 7 2, 7,,, - 5.7 Hz, H8); 8.84, 8.98 (4H, d, Λ.7 = 7.2 Hz, H6); 10.10, 10.19. 10.25 (4H, d, Λ.8 - 5.7 Hz, Hl); 1 1.13, I 1.16 <4H, s, H4).
Example 2 • Preparation of ammonium salts
The following Sal ts woe prepared as described below.
Figure imgf000045_0001
(a) Tetrapyridinium 5
HydroxygalliuiB napbttaaJocyaninέtβtrβsulfonic acid 4 (1S9 tog; 0.17 mrool) was suspended in pyridine/water (50:50; 4 mi) and stirred at room teraporaiure for 16 h during whicb tune the reaction mixture became homogeneous. Emβr/etbanol (86:14, 35 raL) was added to precipitate the βalt and the supernatant liquid was decanted off before etbβr/ethanol (83: 17, 12 mL) w added with stirring. The -olid was filtered off and washed with ether/emanol (50:50, 2 x 5 tnL) and ether (2 x 5 mL). After drying under high vacuum, the tetrapyridituura salt δ was obtained as a green powder (136 mg; 56%). 1H NMR (d*-DMSO) δ 7.7S (8H1 dd, J - 6.3, 6.3 Hz, H3\ Hi'); 7.97, 8.00 (4H, dd, J1A = Ju * 7.2 Hz, H7); 8.25 (4H1 dd, 7 = 7.8, 7.8 Hz, H4'), 8.49 (4H, dd, A7 = 7.2, J g., » 5.7 Hz1 H8); 8.80 (8H, d, J = 7.8 Hz, H2', H6'); 8.84, 8.98 (4H, d, J6J = 7.2 H3. H6); 10.10. 10.19. 10.25 (4R d, ./,^ = 5.7 Hz, H l); 11.13, 11.16 (4H. S. H4).
(b) Tenafπ's(J,8-diazabicyclofS.4.0Jundec-7-enium) 9 - Comparative Example Hydroxygallium naphtbalocyaninetetrasulfonic acid 4 (348 mg; 0.31 mmol) and 1,8- dia2abicyclo(5.4.0]undec.7^ne (DBU) (306 rag; 2.17 ramol) were stirred in methanol (5 mL) for 20 b at room temperature during which time the reaction mixture became homogeneous. The mixture was diluted with ethanol/ether (25:75; 20 mL) and stirred for 30 min. The supernatant was decanted off, ether (20 n»L) was added and the solid was filtered off, washing with ethanol/etber (50:50; 2 x 20 mL), and ether (2 x 20 mL). The tetraammoaium salt 9 was obtained as a green powder after drying under high vacuum (252 mg; 48%). 1H NMR (drDM$O) δ 1.1-1.2 (32H, m, H3 \ H4\ Hi', H10'); 2.5 (8H, m, K6'); 3.0-3.1 (24H, m, H2\ H9\ Hl ! '); 7.97, 8.00 (4H, dd, J n - Ju = 7.2 Hz, H7); 8 49 (4H. dd, Jv = 7.2, / ,., = 5.7 Hz, H8); 8.84, 8.98 (4H, d. J«, = 7-2 Hz, HG); 10.10. 10.19, 10.25 (4H, d, JιΛ - 5.7 Hz, Hl); 1 1.13, 1 ! .16 (4H, s. H4).
(c) Tetrakis(tributylammonium)8 - Comparative Example
Hydroxygallium naphtnalocyaninetetrasulfoαic acid 4 (905 mg; 0.81 mmol) and oibutylamme (2.32 mL; 9.70 mmol) were stirred io ethanol (96%; 5 mL) for 4 75 b ai room temperature during which time the reaction mixture became homogeneous. The solution was diluted with ether (100 mL) and the precipitated solid was filtered off, washing with more ether (2 x 25 mL). Excess amine was removed by stirring the solid in letrabydrofurao/ether (70:30, 40 mL) tbr 2 h and filtering off me solid. The tetralds(tributylanamoniuro) 9alt 8 was dried under high vacuum and obtained as a green powder (730 mg; 49%). This salt is sparingly soluble in water bui readily dissolves Io ethauol. 1H NMR (^DMSO) δ 0.90 (12H, t, J = 7.2 Hz, H41); 1.34 (8H, εxt, J = 7.5 Hz, H31); 1.58 (6H, m, H2'); 3.03 (6H. br dd, J = 7.8, 7.8 Hz, HI 1); 7.97, 8.00 (4H, dd, J ,.» = J1 A = 7.2 Hz, H7), 8 49 (4H, dd, Jv = 7.2, J ,,, = 5.7 Hz, H8); 8.84, 8 98 (4H, d, J^1 = 7.2 Hz. H6); 10.10, 10.19, 10.25 (4H, d, >/,,e ■ S.7 Hz, Hl); 11.13, 11 16 (4H, β, H4).
(d) Tetraimidazoϋum 7
Hydroxygallium naphthalocyaninetetrasulfonic acid 4 (1.40 g; 1.25 mmol) end imidazole (0596 g; 8.75 mmol) weTβ suspended in memanol/water (80:20; 17.5 mL) and then the resulting green mixture was sttrred at room temperature for 2 h, becoming homogeneous after 1 b. The solution was diluted with diethyl ether (50 mL), stirred for 15 coin, and theo allowed to stand. The supernatant liquid was decanted off and then ether/methanol (50:50; 20 mL) was added with stirring. The solid was filtered off, washing with ether/methanol (50:50; 3 x 20 mL) and ether (2 x 20 mL). The solid was then suspended in methanol/ether (50:50; 20 mL) and stirred for 3 h. Filtration and drying under high vacuum afforded the tetraimidazobum salt 7 as a green powder (1.32 g; 76%). 1H NMR (^DMSO) δ 7.61 (8H. br s, H4\ H5 '); 7.98, 8.02 (4H, dd, j u = Ju = 7.2 Hz, H7); 8.49 (4H, br m, H8); 8.84, 8.98 (4H. d, /M = 12 Hz, H6); 8.91 (4H, br s, H2'); 10.10, 10.19, 10.25 (4H, d. JtΛ = 5.7 Hz, Hl); 1 1.13, (4H. br m, H4).
Example 3 - Preparation of Inks and Reflecfaf\ff fipeftra of Ammonium Salts A solution of each salt was made up in an ink vehicle according to Table 1.
Figure imgf000047_0001
Table 1 Composition of dyelesβ ink vehicles for salt derivatives
The resulting clear green solutions were printed on Celcast matt photoquality iokjet paper (143 gsm) on an Epson C61 uikjet printer and then the reflectance specim were measured on a Cary 5 UV-vis spectrophotometer. Results are given in Table 2.
Figure imgf000047_0002
' Figure 28; Figure 29 Table 2 Relationship between amine component of retrasulfonaie salts, pH of ink made according to Table I, and position ofQ-band
From Table 2, it can be seen that compounds S, and 7, where BH* has a pK, in the range of 4 to 9 and the pH of the ink formulation is between 4 and 6.5, the Q-band of absorption iε greater than 800 am However, for compounds 8 and 9, where BH* has a pK» greater than 9 and the pH of the ink formulation is greater than 6.5, the Q-band is significantly less than 800 nm. Accordingly, compounds 5, and 7 are suitable for formulating inkβ which are Dot too acidic to be compatible with conventional CMYK inks, and which retain strong absorption in the nβar-lR region above 800 run.
Other amine salts of the gallium naphtha tocyanine tecrasulfboate 4 were prepared analogously to those prepared above in Examples 2(aMd), ∞d formulated *s 2 mM solutions in ink vehicle A. The resulting clear green solutions were printed on Celcast matt pbotoquatity uikjet paper (143 gsm) on an Epson C61 inkjet printer and then the reflectβcce βpecn-a were measured oo a Cary 5 UV-vis spectrophotometer. Results are given LQ Table 3.
Figure imgf000048_0001
Table 3 Spectroscopic properties of other ammonium salts
From Table 3, Ii can be seen (bat DABCO and quinoline in a stoichiometric ratio of 4: 1 provide salts, which can be formulated into inks having acceptable reflectance spectra. Stronger bases used is the same ratio are generally unsuitable and result in a significant blue-shilt However, tbe use of fewer equivalents of a stronger base can still provide inks having red-shifted Q-bancU. Example 3(i) uses tnbutylamine in a ratio of 1 : 1 and provides a formulation having a Q-band at 605 am. By contrast, tributylamine in a ratio of 4: 1 (Table 2) provides a formulation having a blue-shifted Q-band at 792 nm.
ExamnU 4 - Preparation and Reflectance Spectra of Inks With Added Carbaxylate Salts Inks according to tbe present inveotioo may also be prepared without isolation of the naphthalocyanine salt-. For example, the tetrasulfbtύc acid 4 may be formulated in an ink vehicle and the pH adjusted using a suitable base or buffer. Examples 4(a) and 4φ) below describe me preparation of inks by addition of carboxylase salts in an ink comprising the tetraulforuc 4.
(a) Lithium/sodium acetate and utrasiύfonic acid 4
The tetrasulfonic acid 4 was made up to 2 mM in ink vehicle B containing 8 mM NaOAc or UOAc. This gave a clear green solution containing 6 (pH 5.1) that was printed otv Celcast matt pbotoquality inkjet paper ( 143 £sm). The reflectance spectrum bad X0-U 806 nm for both sodium and lithium.
(b) EDTA disodium salt and tetrasuffonk acid 4
The tetrasulfonic acid 4 was made up to 1.5 mM in ink vehicle B containing 3 mM ethylenediaminetetraaceric acid (EDTA) disodium salt. This gave a clear green solution (pH 3.7) that was printed on Celcast matt pbotoquality InkJet paper (143 gam). The reflectance spectrum bad Xn^ 805 nm.
Example 5 — Preparation and Reflectance Spectra of Inks Comprising Mixed Salts Inks according to the present invention may also comprise mixed salts. Mixed salts may be advantageous m providing a suitable balance of properties or for tuning the spectroscopic characteristics of a salt. For example, in Example 5(b) the direct addition of three equivalents of p-toluenesulfoαic acid to the tetrakjs(DBUammoniura) salt 9 in the ink formulation lowers the pH from 7.7 to 4.0 and shifts the Q-band to 806 am indicating that protonatioα of the interna) mero-nitrogens ha* taken place.
(a) Tetrasttifonk acid 4 and <etrakia(trtbutyUunmonium) salt B
Solutions of the tetrasultonic acid 4 and the tetrakis(tributylammonium) salt 8 (2 mM in vehicle C) were mixed in the ratios as shown in Table 4. The resulting clear green solutions were printed on Cclcast matt photoquality inkjet paper (143 gsm) with an Epson C61 inkjet printer and me pH and maximum absorptions were measured.
Figure imgf000049_0001
Table 4 Properties of mixed tetrosulfonic acid 4 and the ten-akis(tributytammonium) salt 8 in vehicle C
(b) Tctτakis(DBUanwtomum) salt 9 and p-toluentsuffonk acid
The DBUammonium salt 9 (26.3 rag; 15.2 μmol) and p-tolueneεulfonk acid (8.63 mg; 45.6 μmol) were dissolved in ink vehicle B (11.2 mL) to make up a solution that was 1 36 mM with respect to the napbthalocyanine. This gave a clear green solution (pH 4.0) that was printed on Celcast matt photoquality inkjei paper (143 gsm). The reflectance spectrum had λrø» 806 run (Figure 30).
(c) Imidazolium salt 7 and acetic acid
The tetraimidazolium salt 7 was made up to 1 5 mM in ink vehicle B containing 3 mM acetic acid. This gave a clear green solution (pH S l) that was printed on Celcasi mart photoquality inkjet paper (143 gsm). The reflectance spectrum bad K^, 807 nra (Figure 31 ).
Example 6 - Lightfastness
An Oβratn 250 W metal halide lamp (HQI-EP 250W/D E40) with an intensity of 17,000 lumens, (approximately 70,000 lux) was used to irradiate printed samples positioned at a distance of 9.0 cm from the globe. The industry standard measurement of lightfastness is the tune taken for a sample to fade by 30% under typical indoor lighting conditions. Typical indoor lighting conditions are defined as illumination under a lighting intensity of 500 lux for 10 hours per day.
LiEhtfestness - Time taken to fade by 30% x (70,000 lux / 500 lux) x (24 h / 10 b) = Time taken to fedc by 30% * 336
Figure imgf000049_0002
Figure imgf000050_0001
Table 5 Projected lifetimes of ammonium salts printed on paper.
All inks according to the present invention, with a pH in the range of 3.5 to 7, have excellent ligbtfhstoess. By contrast, roe ink prepared from tetrakis(DBUammonium) 9, having a pH of 7.7, bad poor Ugbtfastnoss with a projected lifetime of only 7.9 years.
This surprising result is a further advantage of the present invention and i» understood to be a result of the protooated macrocycle being less reactive towards singlet oxygen.
Example 7 - Ozonefastness Inks were formulated from a variety of salts using the ink vehicles A, B, C1 D, F, H or I. Ink vehicles AO were described in Table I above. Table 6 below describes ink vehicles D, F, H and I.
Figure imgf000050_0002
Tabl* 7 Composition of dyelβss ink vehicles
Ozonefastness of inks printed on Celcasf man pboioqualiry inkjet paper ( 143 gsm) were tested a* follows. The printed samples were exposed to ozone at a concentration of 1 ppm until the intensity at 810 am had decreased to 70%. 1F' denotes a final result for samples that had reached 70% intensity. Other samples had intensity >70% during the test period end the ozone lifetime was extrapolated from acquired data.
Figure imgf000051_0001
Table 8 - Ozonefasiness of printed inks
Inks according to the present invention were βhown to have acceptable ozonefeseness, in addition to acceptable ligbtrastαess.
ID conclusion, gallium napnthalocyanine salts and ink fbnnulaiioos of the present invention are excellent for use with αetpage and Hyperlabel™ systems. These dyes and inks exhibit near-IR absorpcion above 800 tun, good solubility id inkjet ink formulations, negligible or low visibility and excellent light&itocii. Moreover, these dyes can be prepared in a rugh>y>elding, expedient and efficient synthesis.

Claims

1. An aqueous formulation comprising an IR-absorbing aapbtbalocyanine dye of formula (H).
Figure imgf000052_0001
or a salt form thereof, wherein:
M iS Ga(A1);
A1 is an axial ligβnd selected from -OH, halogen, -OR3, -OC(O)R4 or -O(CHjCH2O)cH.c wherein e 19 an integer from 2 to 10 and R' is H, C,., alkyl or C(O)C,α alkyl;
R1 and R2 may be the same or different and are selected from hydrogen or C,.u alkoxy; R3 is selected from C1. ,2 alkyl, C5-I2 aryl. C5.,, arylalkyl or Si(JO(RO(R1);
K4 is selected from C|.« alkyl, C$.n aryl or C5. u arylalkyl; and
R', Ry and R* may be the 9ame or different and are selected from C,.,z alkyl, C1.^ aryl, Cj.i2 arylalkyl, CVu alkoxy, C3-I2 aryloxy or CMJ arylalkoxy; said formulation having a pH in the range of 3.5 to 7.
2. The formulation of claim 1 having a pH in the range of 4 to 6.5.
3. The formulation of claim 1 , wherein aaid formulation is buffered
4. The formulation of claim 1 further comprising at least one base B, wherein a conjugate acid B(T of said at least one base B has a pK, of between 4 and 9.
5. Tho formulation of claim 4, wherein a conjugate acid BH* of said at least one base B has a pK, of between 4.5 and 8.
6. The formulation of claim 4 comprising a nitrogeα ba$e, an oxyanion base or mixtures thereof.
7. The formulatioo of claim 6, wherein said nitrogen baεe is a nitrogen-containing Cj-u heteroaryl base.
8. The formulation of claim 7, said nitrogen base is imidazole or pyridine.
9. The formulation of claim 6, wherein said oxyanic-n base is a carboxylate base.
10. The formulation of claim 9, wherein said carboxylate base is of formula R5C(O)O', wherein R3 is selected from C,.,: alkyl, C$.|3 aryl or Cj.,2 arylalkyl.
1 1. The formulation of claim 4 comprising a nitrogen base and an oxyanion base.
12. The formulation of claim 1, wherein R1 and R2 are both H.
13. The formulation of claim 1, wherein M is Ca(OH).
14. An inkjet ink comprising a formulation according to claim 1.
15. An inkjet ink comprising a dye according to claim 1, wherein said ink has a X1n, of 800 nm or more.
16. An inkjei printer comprising a printhead in fluid communication with at least one ink reservoir, wherein said at least one ink reservoir comprises an inkjet ink according to claim 14.
17. An ink cartridge for an iαkjet printer, said ink cartridge comprising an inkjet ink according to claim 14.
18. A substrate having an ink according to claim 14 disposed thereon.
19. A method of enabling entry of data into a computer system via a printed form, the form containing human-readable Information and machine-readable coded data, the coded data being indicative of an identity of the form and of a plurality of locations on the form, the method including the steps of: receiving, in the computer system and from a sensing device, indicating data regarding the identity of the form and a position of the sensing device relative to the form, the sensing device, when placed in an operative position relative to the form, generating the indicating data using at least some of me coded data; identifying, in the computer system and from the indicating data, at least one field of the form; and interpreting, in the computer system, at least some of the indicating data as it relates to the at least one field, wherein said coded data is printed using aa ink according to claim 14.
20. A method of interacting with a product item, the product item having a printed surface containing human-readable information and machine-readable coded data, the coded data being indicative of an identity of the product item, the method including the steps of:
(a) receiving, in the computer system and from a sensing device, indicating data regarding the identity of the produce item, the sensing device, when placed in an operative position relative to the product item, generating the indicating data using at least some of the coded data; and
Cb) identifying, in the computer system and using the indicating data, an interaction relating to the product item, wherein said coded data is printed using an ink according to claim 14.
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