CA2023919C - Light-stabilised ink compositions - Google Patents
Light-stabilised ink compositionsInfo
- Publication number
- CA2023919C CA2023919C CA002023919A CA2023919A CA2023919C CA 2023919 C CA2023919 C CA 2023919C CA 002023919 A CA002023919 A CA 002023919A CA 2023919 A CA2023919 A CA 2023919A CA 2023919 C CA2023919 C CA 2023919C
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- CA
- Canada
- Prior art keywords
- group
- hydrogen
- formula
- compound
- so3x
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
-
- 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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
Abstract
2-(2'-Hydroxyphenyl)benzotriazoles of formula 1 (see formula I) wherein R1, R2 and R3 are as defined in claim 1, and which contain at least one -SO3X
group in the molecule, are suitable light stabilising additives for aqueous ink compositions, especially for ink jet printing. Some of these compounds are novel compounds.
group in the molecule, are suitable light stabilising additives for aqueous ink compositions, especially for ink jet printing. Some of these compounds are novel compounds.
Description
l.iqht-stabilised ink compositions The present invention relates to aqueous ink compositions which contain a water-soluble derivative of a 2-(2'-hydroxyphenyl)benzotriazole. These ink compositions are particularly suitable for ink jet printing. The invention further relates to novel sulfonated 2-(2'-hydroxyphenyl)benzotriazoles.
Printing by ink jet printing is a very rapid printing method which is controlled by electrical signals. This method comprises jetting fine ink droplets through an orifice on to the recording material. The ink used is preferably an aqueous solution of a water-soluble dye. The dye will normally have a lower lightfastness than the dyestuff pigments used in conventional printing methods. The consequence is that the prints obtained have only a limited storage life when exposed to light.
The proposal has therefore already been made (USP 4 256 493) to add a water-soluble UV absorber of the sulfonated hydroxybenzophenone type to the ink. The metal salts of such compounds have also been proposed as light stabilising additives for ink jet printing inks (JP A-46277/88).
The drawback of such benzophenone derivatives and their salts is that they cause discolourations when added to specific dyes, especially black dyes.
Carboxylic acid derivatives of UV absorbers of the benzotriazole type have also been proposed in Research Disclosure 22 519 [Use of UV-absorbers, P. Tschopp, Ciba-Geigy AG, Basle (1983)) for stabilising dyes and inks. However, these derivatives are not sufficiently soluble in aqueous systems.
It has now been found that specific water-soluble derivatives of 2-(2'-hydroxyphenyl)benzotriazoles are readily suitable light stabilising additives for aqueous ink compositions, especially for ink jet printing.
Specifically, the invention relates to aqueous ink compositions which contain, as light stabiliser, at least one compound of formula I
-z-Ho N R
Rl J r ~,, N
~N~ R3 wherein Rl is hydrogen, halagen, Ct-Cnalkyl, Cl-Gaalkoxy, -COO-R~-OS03X, -COOX
or -SO3X, R2 is hydrogen, OH, Cl-CBalkyl, CS-C6cycloalkyl, phenyl, naphthyl, C7-Cl2aralkyl, ' halogen, Cl-Cgalkoxy or a -Y-Z group, R3 is hydrogen, Cl-CBalkyl, a -Y-Z group or a -Y-O-Z' group, X is hydrogen or M, M is Li, Na, K, z Mg, ~ Ca, z Zn, i Co (II), 2 Cu (Ii), z Ni (II), 3 Cr (III), ; Fe (III), R'i\ / R6 R R4 ~ R4~. ~ i R6 R ~~N~R ~ '1°N ~ R jN O ar i RSs, ~ ~R7 , wherein R4, R5, R6 7 R5 ~~ 5 and R~ are each independently of one another hydrogen, C1-Cl2alkyl, hydroxyethyl, cyclo-hexyl, phenyl or benzyl, Y is a direct bond or a divalent group of one of the following formulae:
-Rg-, -Rg-CONI-I-Rg-, Rg-CON-R~o-r --i H-R8-~ - Rg ~ , -Rg-COO-R9-~ ._ ~I~--Z COOX
~10 Z
-Rg-SOZ-R~-, -R8-S02NH-R~-, , -R8-COO-CfF-R9-- or -Rg-COO-G-Rg-Rlp-Z Rtt-Z
wherein R8, R9, Rlo and R11 are each independently of one another Cl-CZQalkylene which may be substituted by 1-10 hydroxyl groups or are CZ-C2oalkylene which is intemapted by i-10 -O- or -NH-, and 2 is a -COOX or -S03X group, and Z' is -S03X, with the proviso that the compound of formula I contains at least one group of formula -COOX or -SO3X.
Rt as Ct-C~alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tort-butyl. R~ and R3 as C1-C$alkyl may ful°ther be n-pentyl, sec-pentyl, tort-pentyl, n-hexyl, isollexyl, 2-ethylbutyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl or tent-octyl.
Rh-R7 as Ct-Ct2alkyl may additionally be n-decyl, n-dodecyl or isononyl.
R2 as cycloalkyl or aryl may be cyclopentyl, cyclohexyl, phenyl or naphthyl.
R2 as aralkyl -~ 3 -may be benzyl, «-methylbenzyl, «,«-dimethylbenzyl or naphthylmethyl.
Rt as Ct-C~alkoxy may be methoxy, ethoxy, isopropoxy or butoxy. R2 as Ct-CBalkoxy may be additionally be pentyloxy, hexyloxy, heptyloxy or octyloxy.
R$ as Ct-CBalkylene may be unbranched or branched alkylene, such as methylene, di-, tri-, tetra-, penta-, hexa- and octamethylene, 1,2-propylene or 2-rnethyltetramethylene. R9, Rio and Rt l as Ct-CZOalkylene may additionally be octa-, dace-, dodeca-, hexadeca- or octadecamethylene. Preferably R8, R9, Rlo and R11 are Ct-C4alkylene.
R8, R9, Rto and Rtt as alkylene which is interrupted by -O- may be 3-oxatetramethylene, 3,6-dioxaoctamethylene, 3,6,9,12-tetraoxatetradecamethylene or radicals of formulae -f-OC2Ha -~~- and '~OC2Ha ~. R~, Rto and Rtt as OH-substituted alkylene may be in particular 2-hydroxytrimethylene.
The ink compositions preferably contain, as light stabiliser, a compound of formula I, wherein Rt is hydrogen, halogen, Ct-Caalkyl, Ct-C~alkoxy, -COO-R~-OS03X, -COOX or'-S03X, R2 is hydrogen, Ct-C$alkyl, C~-C9phenylalkyl or a -Y-2 group, R3 is hydrogen, Cl-C4alkyl, -Y-2 group or a -Y-O-Z' group, X is hydrogen or M, R R6 R~
M is Li, Na, K, ~~~ , R ,N or eN~~ , wherein Ra, R5, R6 and RS R7 Rg ~~ RS
R7 are each independently of one another H, C1-C~alkyl or hydroxyethyl, Y is a direct bond or a group selected from -R8-, -R~-CONH-R~-, ~8'CON-R~-~zo.-z -R8 ~ , -Rg-C~O-R~- aI'-'R8-COO-CI-~-R9-~1(r-'Z
wherein RH is Ct-C~alkylcne and R~ and Rto are each independently of the other Ct-Ctoalkylene which may be substituted by 1 or 2 hydraxyl groups ar C2-Czoalkylene which is interrupted by 1-10 -O-, and Z is a -COOX or -SOX group and is Z' -S03X, especially those compounds of formula I, wherein Rt is hydrogen, chloro, -CO~'OC2I-Ia r,~ OSO~X, -COOX or -SO3X, R2 is hydrogen, Ct-Cgalkyl, C~-C~phenylalkyl or a -Y-Z group, R3 is hydrogen or a -Y-Z group and x is an integer from Z to 8.
Particularly preferred ink compositions are those containing a compound of formula I, wherein Rt is hydrogen, chloro, -CO-f--OC~I-I4 -~-X -OS03X, -COOX or -503X, R2 is hydrogen, Ct-Cgalkyl, C~-C9phenylalkyl or a -Y-Z group, R3 is hydrogen or a -Y-Z group, x is an integer from 2 to 8, R'~.N / R6 XisLi,Na,Kor i ~ , Y is a direct bond or a group selected from -Rg-, -Rg-CONH-R9-, - Rg ~ or -Rg-COO-R9- , Z is a -COOK or -SO3X group, R4, Rs, R6 and R7 are each independently of one another Ct-C~alkyl or hydroxyethyl, Rg is Ct-C6alkylene and R9 is Ct-Clpalkylene which may be substituted by 1 or hydroxyl groups or is C2-C2aalkylene which is interrupted by 1-10 -O. -X is preferably Li, Na, K, NHh or tetraalkylammonium and is most preferably lithium.
The compounds of formula I preferably contain two -COOX or -S03X groups, most preferably two -S03X groups.
Ra is preferably in ortho-position and R3is preferably in para-position to the hydroxyl group of the hydroxylphenyl radical in formula I.
Illustrative of individual compounds of formula I are:
CIO C(CH3~
N
/ ~ ~N , Li03S ' Nr SC3l.,i za~~~.~
_5-IIO
N
~ vN .~.
a /
NaOgS ~ N
S03Na S03Li HO C
~ ~ ~ ~ \C3-I3 N
WN/ ~ CH3 CFIg S03Li HO S03Na N
~ ~N
Na03S ' N
CHI
HO C(CHg)3 N
a /N CH2SOgLi CI N
CHZS03Li CHI
I
HO CH- CZI-Ig N
N
y/ CI-I2CHZCOOLi CHZCHZCON
CII2CH2COOLi ~0~3~~~
HO \ ; ~ ~ S03Na eN\ CH3 N
a N~~ CH3 S03Na CHg CHg HO \C ~ ~ S03Li a e' i \ CII3 N l \ ~'N~ CHg C, ~ ~ S03Li .s HO C(CHg)3 N
a \N
NH403S \ NS
CHI
l HO CH- C2Hg N
/ a \N
Li00C ~ N
S03Na CI-Ig I
HO CH- CZI-IS
N
a \N
Li00C ~ ~N/
S03Li CHg I
IEO CH-C2Hs N
/ a \N
C1 \ N
SOgLi zo~~o~o fI0 C(CH3r3 N
/ s aN
KOOC N
eCHZCI-IZCOOK
SOgLi HU \C
N 'CH3 ~N
Li03S N / H3 C
CHg a SO3Li CHg I
HO C - (CH2)g-C02H
t / /N' ~ CHI
N ~ 3N(trH2CH20H)~
H02C ~ \N~ CI-I3 _ C - (CHZy3-CO2H
HO C - (CH2)3-COZLi / /N~ ~ '' CHI
N
Li03S ' SN~ CH3 C - (CH2y3-C02Li CHg ~N~
N
\, \N~
SOaLi _g_ HO
/ %N~~, ~ /
\N/
CH2CH2CO.o-øw CI-12CII2-O-~- SO3Li IIo / % ~N /
CI ~ \N/
~CFI2CI-I2C0~-(-CHZCHZ-O~-SOgLi I
HO C - (CHZy3-C02-CH2CH2-O-S03Li / ~N~ / 'CH3 ~.N,i''~.~ CH3 C --- (CH2)3-CUZ-CH2CH2-O-SOgLi CHg Ha / %~
Li03S--~O-CH2CH2)g-U-C \ \N/
O
CHg HU C- (C.H2~-CU2-(-CI-I2CH2-O~S03Li / ~ ~ / \ CHg ~Nf CHg The eligible compounds of the invention contain at least one carboxylic acid or sulFanic acid group or salts thexeoF. Campounds containing two carboxylic acid groups are already known (GB patent 9~ 1 539, French ,patent 1 370 BIA~). '1 he other compounds are novel compounds and likewise constitute an object of the invention.
Accordingly, the invention also relates to compounds of formula I' HO
R1 / i \ ~ R2 I, N ' wherein Rl is hydrogen, halogen, Cl-C4allcyl, Cl-C4alkoxy, -COO-Rg-OS03X, -COOM or -SO3X, R2 is hydrogen, OH, Cl-Csallcyl, CS-C6cycloalkyl, phenyl, naphthyl, C~-Cl2aralkyl, halogen, Cl-Csalkoxy or a -Y-Z group, R3 is hydrogen, Ci-Csalkyl or a -Y-Z group, X is hydrogen or M, M is Li, Na, K, ~ Mg, i Ca, ~ Zn, ~ Co (II), Z Cu (II), 2 Ni (II), ~ Cr (IIIJ, 3 Fe (III), R~N / R6 R4~ R~ I~ R~ ~ i R6 , ~ or z RS \ R~ ' RS N RS ~ ~ Rg ~ ~ R~ ~ wherein R4, Rg, R6 and R~ are each independently of one another hydrogen, Cl-Cl2alkyl, hydroxyethyl, cyclohexyl, phenyl or benzyl, X is hydrogen or M, Y is a group selected from -R8-, -R8-CONH-Itg-, -RS-CON-R9-, -i H-R8-~lp-Z COOX
-Rg-COO-R9-, -R8-SO2-R9-, -Rg-S02NH-Rg-, -R8-COO-CIA-Rg- , --R8 ~ / or Rlp-Z
i lo-z ~s-coo-~R9-, wherein ~11-z R8, R9, Rlo and R11 are each independently of one another Cl-C2palkylene which may be substituted by 1-10 hydroxyl groups or C2-CZOalkylene which is interrupted by 1-10 -O- or and Z is a -COOM or -S03X group, with the proviso that the compound of formula I' contains at least one -COOX group and/or at least one -S03X group.
These compounds can be prepared by methods analogous to those for preparing other 2-(2-hydroxyphenyl)benzotriazoles from the diazonium salts of the corresponding o-nitroanilines by coupling to the corresponding substituted phenols and reduction of the resultant azo compound by cyclisation according to the scheme:
RI ~ ~ diazonium salt NOz H
g HO
HU R
RI / ~NaN ~ R2 ~ / N N ~ R
\ -.."Nf R3 Rt Alternatively, a sulfonic acid radical Rt, R2 or R3 can also be introduced by sulfonating the corresponding benzotriazole. The sulfanation can be corned out by the conventional methods of sulfonaiing aromatic compounds, for example with chlorosulfonic acid. A
further alternative method of introducing a sulfonic acid group is the exchange of a tertiary __ alkyl group R2 or R3 by a S03i~ group by heating in concentrated sulfuric acid.
In these syntheses, the products are normally obtained as the free carboxylic or sulfonic acids, from which the corresponding salts can be prepared by neutralisation with a suitable bask for example by neutralisation with a hydroxide, oxide or carbonate, ammonia ar an organic amine.
Those compounds of formula I which contain two -S03X groups are preferred.
Also preferred are compounds of formula I', wherein R1 is hydrogen, Cl, -CO-f-OC2H4 BUS~3X, -COOX ar -S03X, R2 is hydrogen, CI-Csalkyl, C~-Cgphenylalkyl or a -Y-Z group, R~ is hydrogen or a -Y-Z group, R Rs X is Li, lea, K or , x is an integer from 2 to $, Y is a -R$- or -Rx-CUO-R~- group, wherein R$ and R~ are CI-C~alkylene, and Z is a -COOX or -Sl~3X group, with the proviso that the compounds of formula I' contain at least two -St73X groups.
In preferred compounds of formula I', the substituent R2 is in ortho-position and the substituent R3 is in para-position to the hydroxyl group of the hyraroxyphenyl radical.
The compounds of formula I are preferably added to the ink compositions in an amount of 0.01 to 20% by weight, preferably of 0.1 to 10% by weight. They are readily soluble in these concentrations.
The ink compositions are aqueous compositions. They contain at least 30% by weight of water. In addition to water, they may contain (up to 70 % by weight) one or more water-miscible solvents such as ethylene glycol, di- or triethylene glycol, propylene glycol or ethers of such glycols, 1,4-butanediol, thiodiglycol, glycerol and the ethers thereof, polyglycerol, mono-, di- and triethanolamine, propanolamine, dimethyl formamide, di-methyl sulfoxide, dimethyl acetarnide, N-methylpyrrolidone, methanol, ethanol, isa-propanol, n-propanol, diacetone alcohol, acetone, methyl ethyl ketone or propylene carbonate.
The ink compositions preferably captain 50% by weight of water.
The ink compositions contain water-soluble dyes ar mixtures of the dyes known for colouring natural fibres. These dyes may be typically mono-, di- or palyazo dyes, triphenylrriethane dyes, reactive dyes or phthalocyanine dyes. Examples of such dyes are the dyes Acid Red 14, Acid Red 52, Reactive Red 40, Acid Yellow 17, Acid Yellow 23, Direct Yellow 86, Acid Red 35, Acid Red 249, Direct Red 227, Acid Blue 9, 'Direct Blue 86, Direct Blue 199, Food Black 2, Direct Black 19, Direct Black 38, Dixect Black 168 and Sulphur Black 1 listed in the Colour Index. The ink compositions will normally contain 0.5-6 % by weight of dye.
The ink compositions may also contain minor amounts of various modifiers such as binders, surfactants, biacides, corrosion inhlbitoxs, sequestrants, pfI
buffers or conductivity additives.'fhey may also contain further water-soluble light stabilisers.
Normally, however, the addition of one or more stabilisers of formula I to the ink composition will suffice in the practice of this invention.
'fhe stabilised ink compositions of this invention are preferably used far ink jet printing.
They can, however, also be used for all other conventional utilities for inks, for example for felt-tipped pens, ink pads, fountain pens, pen plotters, typewuiter ribbons or as printing inks fax different printing techniques.
Different techniques are used in ink jet printing, depending on the apparatus employed.
Thus, for example, there are drop-on-demand printers, bubble-jei printers, continuous-jet printers or compound jet printers. The stabilised ink compositions of this invention can be used for all these techniques.
The effect of the addition of a compound of formula I to the ink compositions consists in the enhanced Light stability of the printed image produced with the composition. 'The effect can be measured experimentally by rapid exposure of specimen prints in an exposure apparatus, as shown in the Examples herein. Parts and percentages in these Examples are by weight.
The recording materials of this invention, which are preferably used for ink jet printing, consist of a substrate having a surface which is printable by means of an ink jet. The substrate is normally paper or a plastic sheet and is usually coated on one side with a material which is capable of absorbing ink. This layer will preferably contain ~i02 and polyvinyl alcohol.
Uncoated paper can also be used. In this case, the paper acts simultaneously as substrate and ink absorbing layer. Materials made of cellulosic fibres and textile fibre materials such as cotton fabric or blends of cotton and polyacrylamide or polyester, which materials contain compounds of formula I, can also be used for ink jet printing.
The recording materials can also be transparent, as in the case of projection transparencies.
El.lternatively, the compounds of formula I can also be incorporated into recording materials, particularly those suitable for ink-jet printing.
In the first method, the compounds of the formula I can be added directly to the pulp in the paper manufacture.
A second method of application is spraying the substrate with a solution of compounds of _13_ formula i. The solution is in this case an aqueous solution or a solution in a slightly volatile organic solvent. Spraying or impregnating the material with an organic solution of a compound of formula I is especially suitable when using oil-soluble compounds of formula I. The use of emulsions or dispersions is also possible.
Normally, however, a coating composition having affinity for dyes is ypplied to the substrate and the compounds of formula I are added to this composition. The coating compositions normally consist of a solid filler, a binder and conventional additives.
The filler constitutes the bulk of the coating composition. Examples of suitable fillers are Si02, kaolin, talcum, calcium, magnesium or aluminium sileates, gypsum, zeolith, bentonite, diatomaceous earth, vermiculite, starch or the surface-modified Si02 described in JP-A 60-260 377. lVlinor amounts of white pigments such as titanium dioxide, barytes, magnesium oxide, lime, chalk or magnesium carbonate can be used with the filler in the coating composition, provided they do not drastically lower the density of the ink jet print.
Coating compositions suitable for transparent projectable recording materials may not contain any light-scattering particles such as pigments and fillers.
The binder binds the fillers to one another and to the substrate. Typical conventional binders are water-soluble polymers such as polyvinyl alcohol, partially hydrolysed polyvinyl acetate, cellulose ethers, polyvinyl pyrrolidone and copolymers thereof, polyethylene oxide, salts of polyacrylic acid, sodium alginate, oxidised starch, gelatin, casein, vegetable gum, dextrin, albumin, dispersions and polyacrylates or acrylate/rnethacrylate copolymers, lattices of natural or synthetic rubber, poly(meth)acrylamide, polyvinyl ethers, polyvinyl esters, copolymers of malefic acid, melamine resins, urea resins or the chemically modified polyvinyl alcohols disclosed in JP-A 61-134 290 or JP-A 61-134 291.
An additional dye receptor or a mordant which enhances the fixation of the dye to the caating rn<ty be added to the binder, lye receptors for acid dyes are cationic or amphateric. Exemplary of cationic receptors are polymeric ammanium compounds such as polyvinylbenzyltrimethylammonium chloride, pplydiallyldimethylamrnonium chlocrde, polymethacryloxyethyldimethylhydroxyethylammonium chloride, polyvinylbenzylrnethyl-imidazoliurn chloride, polyvinylbenzylpicalinium chloride or polyvinylbenzyltributyl-amt~ronium chloride. Further examples are basic polymers such as poly(dirnethylarnino-ethyl)methacrylate, polyalkylenepolyamines and their condensation products with dicyandiamide, amine/epichlorohydrin polycondensates or the compounds disclosed in JP-A-57-36 692, 57-64 591, 57-187 289, 57-191 084, 58-177 390, 58-208 357, 59-20 696, 59-33 176, 59-96 987, 59-198 i88, 60-49 990, 60-71 796, 60-72 785, 60-161 188, 582, 60-189 481, 60-189 482, 61-l4 979, 61-43 593, 61-57 379, 61-57 380, 61-58 788, 61-61 887, 61-63 477, 61-72 581, 61-95 977, 61-134 291 or in USP 4 547 405 and 4 554 181 as well as in DE-A-3 417 582. An amphoteric dye receptor is, for example, gelatin.
The coating having affinity for dyes may contain a number of other additives such as antioxidants, further light stabilisers (also including UV absorbers which do not conform to the light stabilisers of this invention), viscosity improvers, fluorescent whitening agents, biocides and/or antistatic agents.
Representative examples of particularly suitable antioxidants are sterically hindered phenols and hydroquinones, for example the antioxidants disclosed in GB-A 2 088 777 or J.P-A-60-72 785, 60-72 786 and 60-71796.
Representative examples of particularly suitable light stabilisers are orgarzic nickel compounds and sterically hindered amines, for example the light stabilisers disclosed in JF-A-58-152 072, 61-146 591, 61-163 886, 60-72 785 and 61-146 S91 or in GB-A-2 088 ?77, JP 59-169 883 and 61-177 279.
Suitable UV absorhers which may be added to a coating composition in conjunction with compounds of formula I are disclosed, for example, in Research Disclosure No.
(1984) page 284, GB-A-2 088 777 and EP-A-0 280 650. Suitable UV absorbers for concurrent use with compounds of formula I in recording substrates for ink jet printing are in particular those of the 2-hydroxyphenylbenzotriazole class and, most particularly, 2-(2'-hydxoxy-3',5'~-di-t-ainylphenyl)benzotriazale and 2-(2'-hydroxy-3'-t-butyl-5'-poly-glycolprapionate-phenyl)benzotriazale. The UV absorbers can be added to the coating composition as emulsion or dispersion. If the compound of formula I is an acid, it cart be dissolved in the coating composition by addition of alkali. Compounds of forxrzula I which are not acids cats be dissolved either direct in the coating composition or are added to it in the faun of an emulsion or suspension.
The coating composition is normally applied to the substrate, for example paper, and dried by hearing. As already mentioned, the compounds of formula I can be also applied to the recording substrate in a separate operation, alone or together with other already described components, as aqueous solution. Application can be made by spraying, by sizing in a sizing press, by a separate coating operation or by immersion in a vat. After subjecting the recording substrate to such an aftertreatrnent, an additional drying step is necessary.
The recording substrate preferably contains 1 to 10000 rng/mz, most preferably 50 bis 2000 mgt, of at least one compound of formula I.
Example 1: A coating composition based on silica/polyvinyl alcohol is prepared from the following components:
16.34 g of a 10% solution of polyvinyl alcohol (Riedel de I-Iaen GmbH) 0.02 g of di-tert-octylphenylpolyethylene oxide 2.00 g of silica (Type 244, W.R. Grace and Co.) 9.54 g of water.
The resultant coating composition is dispersed by ultrasonication and filtered through a sieve of polyester fibxes having a mesh size of 24 um. The pH is adjusted to 7.0 by addition of 2N sodium hydroxide solution.
The coating composition is applied with a wire applicator to photographic paper in a thickness of 36 wm. After drying with warm air, the coating has a dry weight of ca.
Printing by ink jet printing is a very rapid printing method which is controlled by electrical signals. This method comprises jetting fine ink droplets through an orifice on to the recording material. The ink used is preferably an aqueous solution of a water-soluble dye. The dye will normally have a lower lightfastness than the dyestuff pigments used in conventional printing methods. The consequence is that the prints obtained have only a limited storage life when exposed to light.
The proposal has therefore already been made (USP 4 256 493) to add a water-soluble UV absorber of the sulfonated hydroxybenzophenone type to the ink. The metal salts of such compounds have also been proposed as light stabilising additives for ink jet printing inks (JP A-46277/88).
The drawback of such benzophenone derivatives and their salts is that they cause discolourations when added to specific dyes, especially black dyes.
Carboxylic acid derivatives of UV absorbers of the benzotriazole type have also been proposed in Research Disclosure 22 519 [Use of UV-absorbers, P. Tschopp, Ciba-Geigy AG, Basle (1983)) for stabilising dyes and inks. However, these derivatives are not sufficiently soluble in aqueous systems.
It has now been found that specific water-soluble derivatives of 2-(2'-hydroxyphenyl)benzotriazoles are readily suitable light stabilising additives for aqueous ink compositions, especially for ink jet printing.
Specifically, the invention relates to aqueous ink compositions which contain, as light stabiliser, at least one compound of formula I
-z-Ho N R
Rl J r ~,, N
~N~ R3 wherein Rl is hydrogen, halagen, Ct-Cnalkyl, Cl-Gaalkoxy, -COO-R~-OS03X, -COOX
or -SO3X, R2 is hydrogen, OH, Cl-CBalkyl, CS-C6cycloalkyl, phenyl, naphthyl, C7-Cl2aralkyl, ' halogen, Cl-Cgalkoxy or a -Y-Z group, R3 is hydrogen, Cl-CBalkyl, a -Y-Z group or a -Y-O-Z' group, X is hydrogen or M, M is Li, Na, K, z Mg, ~ Ca, z Zn, i Co (II), 2 Cu (Ii), z Ni (II), 3 Cr (III), ; Fe (III), R'i\ / R6 R R4 ~ R4~. ~ i R6 R ~~N~R ~ '1°N ~ R jN O ar i RSs, ~ ~R7 , wherein R4, R5, R6 7 R5 ~~ 5 and R~ are each independently of one another hydrogen, C1-Cl2alkyl, hydroxyethyl, cyclo-hexyl, phenyl or benzyl, Y is a direct bond or a divalent group of one of the following formulae:
-Rg-, -Rg-CONI-I-Rg-, Rg-CON-R~o-r --i H-R8-~ - Rg ~ , -Rg-COO-R9-~ ._ ~I~--Z COOX
~10 Z
-Rg-SOZ-R~-, -R8-S02NH-R~-, , -R8-COO-CfF-R9-- or -Rg-COO-G-Rg-Rlp-Z Rtt-Z
wherein R8, R9, Rlo and R11 are each independently of one another Cl-CZQalkylene which may be substituted by 1-10 hydroxyl groups or are CZ-C2oalkylene which is intemapted by i-10 -O- or -NH-, and 2 is a -COOX or -S03X group, and Z' is -S03X, with the proviso that the compound of formula I contains at least one group of formula -COOX or -SO3X.
Rt as Ct-C~alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tort-butyl. R~ and R3 as C1-C$alkyl may ful°ther be n-pentyl, sec-pentyl, tort-pentyl, n-hexyl, isollexyl, 2-ethylbutyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl or tent-octyl.
Rh-R7 as Ct-Ct2alkyl may additionally be n-decyl, n-dodecyl or isononyl.
R2 as cycloalkyl or aryl may be cyclopentyl, cyclohexyl, phenyl or naphthyl.
R2 as aralkyl -~ 3 -may be benzyl, «-methylbenzyl, «,«-dimethylbenzyl or naphthylmethyl.
Rt as Ct-C~alkoxy may be methoxy, ethoxy, isopropoxy or butoxy. R2 as Ct-CBalkoxy may be additionally be pentyloxy, hexyloxy, heptyloxy or octyloxy.
R$ as Ct-CBalkylene may be unbranched or branched alkylene, such as methylene, di-, tri-, tetra-, penta-, hexa- and octamethylene, 1,2-propylene or 2-rnethyltetramethylene. R9, Rio and Rt l as Ct-CZOalkylene may additionally be octa-, dace-, dodeca-, hexadeca- or octadecamethylene. Preferably R8, R9, Rlo and R11 are Ct-C4alkylene.
R8, R9, Rto and Rtt as alkylene which is interrupted by -O- may be 3-oxatetramethylene, 3,6-dioxaoctamethylene, 3,6,9,12-tetraoxatetradecamethylene or radicals of formulae -f-OC2Ha -~~- and '~OC2Ha ~. R~, Rto and Rtt as OH-substituted alkylene may be in particular 2-hydroxytrimethylene.
The ink compositions preferably contain, as light stabiliser, a compound of formula I, wherein Rt is hydrogen, halogen, Ct-Caalkyl, Ct-C~alkoxy, -COO-R~-OS03X, -COOX or'-S03X, R2 is hydrogen, Ct-C$alkyl, C~-C9phenylalkyl or a -Y-2 group, R3 is hydrogen, Cl-C4alkyl, -Y-2 group or a -Y-O-Z' group, X is hydrogen or M, R R6 R~
M is Li, Na, K, ~~~ , R ,N or eN~~ , wherein Ra, R5, R6 and RS R7 Rg ~~ RS
R7 are each independently of one another H, C1-C~alkyl or hydroxyethyl, Y is a direct bond or a group selected from -R8-, -R~-CONH-R~-, ~8'CON-R~-~zo.-z -R8 ~ , -Rg-C~O-R~- aI'-'R8-COO-CI-~-R9-~1(r-'Z
wherein RH is Ct-C~alkylcne and R~ and Rto are each independently of the other Ct-Ctoalkylene which may be substituted by 1 or 2 hydraxyl groups ar C2-Czoalkylene which is interrupted by 1-10 -O-, and Z is a -COOX or -SOX group and is Z' -S03X, especially those compounds of formula I, wherein Rt is hydrogen, chloro, -CO~'OC2I-Ia r,~ OSO~X, -COOX or -SO3X, R2 is hydrogen, Ct-Cgalkyl, C~-C~phenylalkyl or a -Y-Z group, R3 is hydrogen or a -Y-Z group and x is an integer from Z to 8.
Particularly preferred ink compositions are those containing a compound of formula I, wherein Rt is hydrogen, chloro, -CO-f--OC~I-I4 -~-X -OS03X, -COOX or -503X, R2 is hydrogen, Ct-Cgalkyl, C~-C9phenylalkyl or a -Y-Z group, R3 is hydrogen or a -Y-Z group, x is an integer from 2 to 8, R'~.N / R6 XisLi,Na,Kor i ~ , Y is a direct bond or a group selected from -Rg-, -Rg-CONH-R9-, - Rg ~ or -Rg-COO-R9- , Z is a -COOK or -SO3X group, R4, Rs, R6 and R7 are each independently of one another Ct-C~alkyl or hydroxyethyl, Rg is Ct-C6alkylene and R9 is Ct-Clpalkylene which may be substituted by 1 or hydroxyl groups or is C2-C2aalkylene which is interrupted by 1-10 -O. -X is preferably Li, Na, K, NHh or tetraalkylammonium and is most preferably lithium.
The compounds of formula I preferably contain two -COOX or -S03X groups, most preferably two -S03X groups.
Ra is preferably in ortho-position and R3is preferably in para-position to the hydroxyl group of the hydroxylphenyl radical in formula I.
Illustrative of individual compounds of formula I are:
CIO C(CH3~
N
/ ~ ~N , Li03S ' Nr SC3l.,i za~~~.~
_5-IIO
N
~ vN .~.
a /
NaOgS ~ N
S03Na S03Li HO C
~ ~ ~ ~ \C3-I3 N
WN/ ~ CH3 CFIg S03Li HO S03Na N
~ ~N
Na03S ' N
CHI
HO C(CHg)3 N
a /N CH2SOgLi CI N
CHZS03Li CHI
I
HO CH- CZI-Ig N
N
y/ CI-I2CHZCOOLi CHZCHZCON
CII2CH2COOLi ~0~3~~~
HO \ ; ~ ~ S03Na eN\ CH3 N
a N~~ CH3 S03Na CHg CHg HO \C ~ ~ S03Li a e' i \ CII3 N l \ ~'N~ CHg C, ~ ~ S03Li .s HO C(CHg)3 N
a \N
NH403S \ NS
CHI
l HO CH- C2Hg N
/ a \N
Li00C ~ N
S03Na CI-Ig I
HO CH- CZI-IS
N
a \N
Li00C ~ ~N/
S03Li CHg I
IEO CH-C2Hs N
/ a \N
C1 \ N
SOgLi zo~~o~o fI0 C(CH3r3 N
/ s aN
KOOC N
eCHZCI-IZCOOK
SOgLi HU \C
N 'CH3 ~N
Li03S N / H3 C
CHg a SO3Li CHg I
HO C - (CH2)g-C02H
t / /N' ~ CHI
N ~ 3N(trH2CH20H)~
H02C ~ \N~ CI-I3 _ C - (CHZy3-CO2H
HO C - (CH2)3-COZLi / /N~ ~ '' CHI
N
Li03S ' SN~ CH3 C - (CH2y3-C02Li CHg ~N~
N
\, \N~
SOaLi _g_ HO
/ %N~~, ~ /
\N/
CH2CH2CO.o-øw CI-12CII2-O-~- SO3Li IIo / % ~N /
CI ~ \N/
~CFI2CI-I2C0~-(-CHZCHZ-O~-SOgLi I
HO C - (CHZy3-C02-CH2CH2-O-S03Li / ~N~ / 'CH3 ~.N,i''~.~ CH3 C --- (CH2)3-CUZ-CH2CH2-O-SOgLi CHg Ha / %~
Li03S--~O-CH2CH2)g-U-C \ \N/
O
CHg HU C- (C.H2~-CU2-(-CI-I2CH2-O~S03Li / ~ ~ / \ CHg ~Nf CHg The eligible compounds of the invention contain at least one carboxylic acid or sulFanic acid group or salts thexeoF. Campounds containing two carboxylic acid groups are already known (GB patent 9~ 1 539, French ,patent 1 370 BIA~). '1 he other compounds are novel compounds and likewise constitute an object of the invention.
Accordingly, the invention also relates to compounds of formula I' HO
R1 / i \ ~ R2 I, N ' wherein Rl is hydrogen, halogen, Cl-C4allcyl, Cl-C4alkoxy, -COO-Rg-OS03X, -COOM or -SO3X, R2 is hydrogen, OH, Cl-Csallcyl, CS-C6cycloalkyl, phenyl, naphthyl, C~-Cl2aralkyl, halogen, Cl-Csalkoxy or a -Y-Z group, R3 is hydrogen, Ci-Csalkyl or a -Y-Z group, X is hydrogen or M, M is Li, Na, K, ~ Mg, i Ca, ~ Zn, ~ Co (II), Z Cu (II), 2 Ni (II), ~ Cr (IIIJ, 3 Fe (III), R~N / R6 R4~ R~ I~ R~ ~ i R6 , ~ or z RS \ R~ ' RS N RS ~ ~ Rg ~ ~ R~ ~ wherein R4, Rg, R6 and R~ are each independently of one another hydrogen, Cl-Cl2alkyl, hydroxyethyl, cyclohexyl, phenyl or benzyl, X is hydrogen or M, Y is a group selected from -R8-, -R8-CONH-Itg-, -RS-CON-R9-, -i H-R8-~lp-Z COOX
-Rg-COO-R9-, -R8-SO2-R9-, -Rg-S02NH-Rg-, -R8-COO-CIA-Rg- , --R8 ~ / or Rlp-Z
i lo-z ~s-coo-~R9-, wherein ~11-z R8, R9, Rlo and R11 are each independently of one another Cl-C2palkylene which may be substituted by 1-10 hydroxyl groups or C2-CZOalkylene which is interrupted by 1-10 -O- or and Z is a -COOM or -S03X group, with the proviso that the compound of formula I' contains at least one -COOX group and/or at least one -S03X group.
These compounds can be prepared by methods analogous to those for preparing other 2-(2-hydroxyphenyl)benzotriazoles from the diazonium salts of the corresponding o-nitroanilines by coupling to the corresponding substituted phenols and reduction of the resultant azo compound by cyclisation according to the scheme:
RI ~ ~ diazonium salt NOz H
g HO
HU R
RI / ~NaN ~ R2 ~ / N N ~ R
\ -.."Nf R3 Rt Alternatively, a sulfonic acid radical Rt, R2 or R3 can also be introduced by sulfonating the corresponding benzotriazole. The sulfanation can be corned out by the conventional methods of sulfonaiing aromatic compounds, for example with chlorosulfonic acid. A
further alternative method of introducing a sulfonic acid group is the exchange of a tertiary __ alkyl group R2 or R3 by a S03i~ group by heating in concentrated sulfuric acid.
In these syntheses, the products are normally obtained as the free carboxylic or sulfonic acids, from which the corresponding salts can be prepared by neutralisation with a suitable bask for example by neutralisation with a hydroxide, oxide or carbonate, ammonia ar an organic amine.
Those compounds of formula I which contain two -S03X groups are preferred.
Also preferred are compounds of formula I', wherein R1 is hydrogen, Cl, -CO-f-OC2H4 BUS~3X, -COOX ar -S03X, R2 is hydrogen, CI-Csalkyl, C~-Cgphenylalkyl or a -Y-Z group, R~ is hydrogen or a -Y-Z group, R Rs X is Li, lea, K or , x is an integer from 2 to $, Y is a -R$- or -Rx-CUO-R~- group, wherein R$ and R~ are CI-C~alkylene, and Z is a -COOX or -Sl~3X group, with the proviso that the compounds of formula I' contain at least two -St73X groups.
In preferred compounds of formula I', the substituent R2 is in ortho-position and the substituent R3 is in para-position to the hydroxyl group of the hyraroxyphenyl radical.
The compounds of formula I are preferably added to the ink compositions in an amount of 0.01 to 20% by weight, preferably of 0.1 to 10% by weight. They are readily soluble in these concentrations.
The ink compositions are aqueous compositions. They contain at least 30% by weight of water. In addition to water, they may contain (up to 70 % by weight) one or more water-miscible solvents such as ethylene glycol, di- or triethylene glycol, propylene glycol or ethers of such glycols, 1,4-butanediol, thiodiglycol, glycerol and the ethers thereof, polyglycerol, mono-, di- and triethanolamine, propanolamine, dimethyl formamide, di-methyl sulfoxide, dimethyl acetarnide, N-methylpyrrolidone, methanol, ethanol, isa-propanol, n-propanol, diacetone alcohol, acetone, methyl ethyl ketone or propylene carbonate.
The ink compositions preferably captain 50% by weight of water.
The ink compositions contain water-soluble dyes ar mixtures of the dyes known for colouring natural fibres. These dyes may be typically mono-, di- or palyazo dyes, triphenylrriethane dyes, reactive dyes or phthalocyanine dyes. Examples of such dyes are the dyes Acid Red 14, Acid Red 52, Reactive Red 40, Acid Yellow 17, Acid Yellow 23, Direct Yellow 86, Acid Red 35, Acid Red 249, Direct Red 227, Acid Blue 9, 'Direct Blue 86, Direct Blue 199, Food Black 2, Direct Black 19, Direct Black 38, Dixect Black 168 and Sulphur Black 1 listed in the Colour Index. The ink compositions will normally contain 0.5-6 % by weight of dye.
The ink compositions may also contain minor amounts of various modifiers such as binders, surfactants, biacides, corrosion inhlbitoxs, sequestrants, pfI
buffers or conductivity additives.'fhey may also contain further water-soluble light stabilisers.
Normally, however, the addition of one or more stabilisers of formula I to the ink composition will suffice in the practice of this invention.
'fhe stabilised ink compositions of this invention are preferably used far ink jet printing.
They can, however, also be used for all other conventional utilities for inks, for example for felt-tipped pens, ink pads, fountain pens, pen plotters, typewuiter ribbons or as printing inks fax different printing techniques.
Different techniques are used in ink jet printing, depending on the apparatus employed.
Thus, for example, there are drop-on-demand printers, bubble-jei printers, continuous-jet printers or compound jet printers. The stabilised ink compositions of this invention can be used for all these techniques.
The effect of the addition of a compound of formula I to the ink compositions consists in the enhanced Light stability of the printed image produced with the composition. 'The effect can be measured experimentally by rapid exposure of specimen prints in an exposure apparatus, as shown in the Examples herein. Parts and percentages in these Examples are by weight.
The recording materials of this invention, which are preferably used for ink jet printing, consist of a substrate having a surface which is printable by means of an ink jet. The substrate is normally paper or a plastic sheet and is usually coated on one side with a material which is capable of absorbing ink. This layer will preferably contain ~i02 and polyvinyl alcohol.
Uncoated paper can also be used. In this case, the paper acts simultaneously as substrate and ink absorbing layer. Materials made of cellulosic fibres and textile fibre materials such as cotton fabric or blends of cotton and polyacrylamide or polyester, which materials contain compounds of formula I, can also be used for ink jet printing.
The recording materials can also be transparent, as in the case of projection transparencies.
El.lternatively, the compounds of formula I can also be incorporated into recording materials, particularly those suitable for ink-jet printing.
In the first method, the compounds of the formula I can be added directly to the pulp in the paper manufacture.
A second method of application is spraying the substrate with a solution of compounds of _13_ formula i. The solution is in this case an aqueous solution or a solution in a slightly volatile organic solvent. Spraying or impregnating the material with an organic solution of a compound of formula I is especially suitable when using oil-soluble compounds of formula I. The use of emulsions or dispersions is also possible.
Normally, however, a coating composition having affinity for dyes is ypplied to the substrate and the compounds of formula I are added to this composition. The coating compositions normally consist of a solid filler, a binder and conventional additives.
The filler constitutes the bulk of the coating composition. Examples of suitable fillers are Si02, kaolin, talcum, calcium, magnesium or aluminium sileates, gypsum, zeolith, bentonite, diatomaceous earth, vermiculite, starch or the surface-modified Si02 described in JP-A 60-260 377. lVlinor amounts of white pigments such as titanium dioxide, barytes, magnesium oxide, lime, chalk or magnesium carbonate can be used with the filler in the coating composition, provided they do not drastically lower the density of the ink jet print.
Coating compositions suitable for transparent projectable recording materials may not contain any light-scattering particles such as pigments and fillers.
The binder binds the fillers to one another and to the substrate. Typical conventional binders are water-soluble polymers such as polyvinyl alcohol, partially hydrolysed polyvinyl acetate, cellulose ethers, polyvinyl pyrrolidone and copolymers thereof, polyethylene oxide, salts of polyacrylic acid, sodium alginate, oxidised starch, gelatin, casein, vegetable gum, dextrin, albumin, dispersions and polyacrylates or acrylate/rnethacrylate copolymers, lattices of natural or synthetic rubber, poly(meth)acrylamide, polyvinyl ethers, polyvinyl esters, copolymers of malefic acid, melamine resins, urea resins or the chemically modified polyvinyl alcohols disclosed in JP-A 61-134 290 or JP-A 61-134 291.
An additional dye receptor or a mordant which enhances the fixation of the dye to the caating rn<ty be added to the binder, lye receptors for acid dyes are cationic or amphateric. Exemplary of cationic receptors are polymeric ammanium compounds such as polyvinylbenzyltrimethylammonium chloride, pplydiallyldimethylamrnonium chlocrde, polymethacryloxyethyldimethylhydroxyethylammonium chloride, polyvinylbenzylrnethyl-imidazoliurn chloride, polyvinylbenzylpicalinium chloride or polyvinylbenzyltributyl-amt~ronium chloride. Further examples are basic polymers such as poly(dirnethylarnino-ethyl)methacrylate, polyalkylenepolyamines and their condensation products with dicyandiamide, amine/epichlorohydrin polycondensates or the compounds disclosed in JP-A-57-36 692, 57-64 591, 57-187 289, 57-191 084, 58-177 390, 58-208 357, 59-20 696, 59-33 176, 59-96 987, 59-198 i88, 60-49 990, 60-71 796, 60-72 785, 60-161 188, 582, 60-189 481, 60-189 482, 61-l4 979, 61-43 593, 61-57 379, 61-57 380, 61-58 788, 61-61 887, 61-63 477, 61-72 581, 61-95 977, 61-134 291 or in USP 4 547 405 and 4 554 181 as well as in DE-A-3 417 582. An amphoteric dye receptor is, for example, gelatin.
The coating having affinity for dyes may contain a number of other additives such as antioxidants, further light stabilisers (also including UV absorbers which do not conform to the light stabilisers of this invention), viscosity improvers, fluorescent whitening agents, biocides and/or antistatic agents.
Representative examples of particularly suitable antioxidants are sterically hindered phenols and hydroquinones, for example the antioxidants disclosed in GB-A 2 088 777 or J.P-A-60-72 785, 60-72 786 and 60-71796.
Representative examples of particularly suitable light stabilisers are orgarzic nickel compounds and sterically hindered amines, for example the light stabilisers disclosed in JF-A-58-152 072, 61-146 591, 61-163 886, 60-72 785 and 61-146 S91 or in GB-A-2 088 ?77, JP 59-169 883 and 61-177 279.
Suitable UV absorhers which may be added to a coating composition in conjunction with compounds of formula I are disclosed, for example, in Research Disclosure No.
(1984) page 284, GB-A-2 088 777 and EP-A-0 280 650. Suitable UV absorbers for concurrent use with compounds of formula I in recording substrates for ink jet printing are in particular those of the 2-hydroxyphenylbenzotriazole class and, most particularly, 2-(2'-hydxoxy-3',5'~-di-t-ainylphenyl)benzotriazale and 2-(2'-hydroxy-3'-t-butyl-5'-poly-glycolprapionate-phenyl)benzotriazale. The UV absorbers can be added to the coating composition as emulsion or dispersion. If the compound of formula I is an acid, it cart be dissolved in the coating composition by addition of alkali. Compounds of forxrzula I which are not acids cats be dissolved either direct in the coating composition or are added to it in the faun of an emulsion or suspension.
The coating composition is normally applied to the substrate, for example paper, and dried by hearing. As already mentioned, the compounds of formula I can be also applied to the recording substrate in a separate operation, alone or together with other already described components, as aqueous solution. Application can be made by spraying, by sizing in a sizing press, by a separate coating operation or by immersion in a vat. After subjecting the recording substrate to such an aftertreatrnent, an additional drying step is necessary.
The recording substrate preferably contains 1 to 10000 rng/mz, most preferably 50 bis 2000 mgt, of at least one compound of formula I.
Example 1: A coating composition based on silica/polyvinyl alcohol is prepared from the following components:
16.34 g of a 10% solution of polyvinyl alcohol (Riedel de I-Iaen GmbH) 0.02 g of di-tert-octylphenylpolyethylene oxide 2.00 g of silica (Type 244, W.R. Grace and Co.) 9.54 g of water.
The resultant coating composition is dispersed by ultrasonication and filtered through a sieve of polyester fibxes having a mesh size of 24 um. The pH is adjusted to 7.0 by addition of 2N sodium hydroxide solution.
The coating composition is applied with a wire applicator to photographic paper in a thickness of 36 wm. After drying with warm air, the coating has a dry weight of ca.
5.0 g/m2.
The recording material is printed with an ink Composition of this invention which contains a UV absorber of formula I and a comparison ink composition which does not contain a UV absorber.
The ink is prepared as follows:
3 g of a UV absorber of formula ., HO S03Na ~N~ /
(UV ~ w /N
Na03S \ N
are dissolved in a mixture of 83 g of water and 15 g of glycerol. A dye solution is prepared from 4 g of C.I. Food Black 2 in 80 g of water and 15 g of glycerol. Both solutions are filtered through a membrane filter with a pore size of 0.3 wm, and combined.
The printing ink composition so obtained consists of:
81.5 % of water 15 % of glycerol 2 % of dye 1.5 % of UV absorber.
The blank specimen is prepared by combining the dye solution with equal parts of a mixture of 86 g of water and 15 g of glycerol.
The inks are filled into ink cartidges of a Hewlett-Packard "Think-Jet" ink jet printer.
Specimen prints having a density of 192 x 96 dots per inch (75.6 x 37.8 dots per cm2) are prepared.
After storage for 1 week to dry out the print comvletely, the colour density of the specimen prints is measured with a Macbeth TR 924 densitometer using a status A filter.
The specimen prints are then irradiated in an Atlas Weather-O-Meter with a xenon lamp having an intensity of 81 klux behind a filter of 6 mm thick window glass. The colour intensity is measured once more to ascertain the percentage loss of intensity.
The results are reported in the following table. Lower values denote higher lightfastness.
UV absorber Loss of colour density after exposure none 15 %
1.5 % 10 %
*Trade-mark 'The same test is made using sadium 2-hydroxy-4-methoxybenzophenone-5-sulfonate as UV absorber. A discolouration of the black print to brawnish black occurs.
lJxample 2: An ink concentrate consisting of 4 g of C.I. Acid Red, 25 g of cliethylene glycol and 70 g of water, and a UV absorber concentrate consisting of 4 g of UV absorber, 25 g of diethylene glycol and 70 g of water, are prepared. The following compounds are used as UV absorbers:
CHg I
HO CH- CZHS
N
UV II ct a ~N~N
a S03Li and HO C ~ ~ S03Na UV III N
\. N~ CH3 C~ ~ ~ Sp3Na i and, as comparision UV absorbers, the compounds of formulae o tIo II
c VI
~H3 S03Na and off o rto ii c VII
H3co ~' ~' ocH~
SO~Nu SOgNa 2~0~3919 Ink compositions are prepared from I part of dye concentrate and UV absorber concentrate and filled into cartridges of a I-Iewlett Packard Quiet Jet printer. After preparing specimen prints on paper suitable for ink jet printing, the lightfastness of these prints is tested as described in Example 1. The results are reported in Table I.
Table 1:
UV absorberLoss of density (15 kJ/cm2) without 63 %
UV II 50 %
UV III 46 %
VI 59%
V II 69 %
Example 3: As described in Example 2, ink compositions are prepared from the dyes Food Black 2, Acid Red 14, 27, 35 and 249, Direct Red 227 and Reactive Red 24, while the UV
absorber concentrate consists of 6 g of UV absorber, 25 g of diethylene glycol and 7U g of water.
I'a-ior to use, the concentrate containing Reactive Red is adjusted with lithium hydroxide to pH 12.0, heated for 3U minutes at 95-100°C, and subsequently adjusted with sulfuric acid to pH 7.
The prints are prepared and the lightfastness test is carried out as described in Example 2.
The results are reported in Table 2.
N
b ~
r ~ M
b 00 . GO
, op ~D
t~
.
N
U
v N
b O
GyN., ch N
C~
~O
' .~ 4 SM~V~
N
w N
N
O
M
N
~ v~ v~
O N
l~ ~p oo O~
N
Q' 4.
W
c~
d.
S
"Ci .e~".1O OD
~ V7 ri ~I~O~O~
._ N
N
N
Z
O U
Z
'~ x z O
U~
U-U
/
O
r.., U
~ ~M"~d'~i O
Z
p, ~
N .O ''~
r-~
b
The recording material is printed with an ink Composition of this invention which contains a UV absorber of formula I and a comparison ink composition which does not contain a UV absorber.
The ink is prepared as follows:
3 g of a UV absorber of formula ., HO S03Na ~N~ /
(UV ~ w /N
Na03S \ N
are dissolved in a mixture of 83 g of water and 15 g of glycerol. A dye solution is prepared from 4 g of C.I. Food Black 2 in 80 g of water and 15 g of glycerol. Both solutions are filtered through a membrane filter with a pore size of 0.3 wm, and combined.
The printing ink composition so obtained consists of:
81.5 % of water 15 % of glycerol 2 % of dye 1.5 % of UV absorber.
The blank specimen is prepared by combining the dye solution with equal parts of a mixture of 86 g of water and 15 g of glycerol.
The inks are filled into ink cartidges of a Hewlett-Packard "Think-Jet" ink jet printer.
Specimen prints having a density of 192 x 96 dots per inch (75.6 x 37.8 dots per cm2) are prepared.
After storage for 1 week to dry out the print comvletely, the colour density of the specimen prints is measured with a Macbeth TR 924 densitometer using a status A filter.
The specimen prints are then irradiated in an Atlas Weather-O-Meter with a xenon lamp having an intensity of 81 klux behind a filter of 6 mm thick window glass. The colour intensity is measured once more to ascertain the percentage loss of intensity.
The results are reported in the following table. Lower values denote higher lightfastness.
UV absorber Loss of colour density after exposure none 15 %
1.5 % 10 %
*Trade-mark 'The same test is made using sadium 2-hydroxy-4-methoxybenzophenone-5-sulfonate as UV absorber. A discolouration of the black print to brawnish black occurs.
lJxample 2: An ink concentrate consisting of 4 g of C.I. Acid Red, 25 g of cliethylene glycol and 70 g of water, and a UV absorber concentrate consisting of 4 g of UV absorber, 25 g of diethylene glycol and 70 g of water, are prepared. The following compounds are used as UV absorbers:
CHg I
HO CH- CZHS
N
UV II ct a ~N~N
a S03Li and HO C ~ ~ S03Na UV III N
\. N~ CH3 C~ ~ ~ Sp3Na i and, as comparision UV absorbers, the compounds of formulae o tIo II
c VI
~H3 S03Na and off o rto ii c VII
H3co ~' ~' ocH~
SO~Nu SOgNa 2~0~3919 Ink compositions are prepared from I part of dye concentrate and UV absorber concentrate and filled into cartridges of a I-Iewlett Packard Quiet Jet printer. After preparing specimen prints on paper suitable for ink jet printing, the lightfastness of these prints is tested as described in Example 1. The results are reported in Table I.
Table 1:
UV absorberLoss of density (15 kJ/cm2) without 63 %
UV II 50 %
UV III 46 %
VI 59%
V II 69 %
Example 3: As described in Example 2, ink compositions are prepared from the dyes Food Black 2, Acid Red 14, 27, 35 and 249, Direct Red 227 and Reactive Red 24, while the UV
absorber concentrate consists of 6 g of UV absorber, 25 g of diethylene glycol and 7U g of water.
I'a-ior to use, the concentrate containing Reactive Red is adjusted with lithium hydroxide to pH 12.0, heated for 3U minutes at 95-100°C, and subsequently adjusted with sulfuric acid to pH 7.
The prints are prepared and the lightfastness test is carried out as described in Example 2.
The results are reported in Table 2.
N
b ~
r ~ M
b 00 . GO
, op ~D
t~
.
N
U
v N
b O
GyN., ch N
C~
~O
' .~ 4 SM~V~
N
w N
N
O
M
N
~ v~ v~
O N
l~ ~p oo O~
N
Q' 4.
W
c~
d.
S
"Ci .e~".1O OD
~ V7 ri ~I~O~O~
._ N
N
N
Z
O U
Z
'~ x z O
U~
U-U
/
O
r.., U
~ ~M"~d'~i O
Z
p, ~
N .O ''~
r-~
b
Claims (14)
1. An aqueous ink composition comprising a) at least 30 % by weight of water, and b) an effective coloring amount of a water soluble dye, and, as light stabiliser, c) 0.01 to 20 % by weight, based on the total solution, of at least one compound of formula I
wherein R1 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, -COO-R9-OSO3X or -R2 is hydrogen, OH, C1-C8alkyl, C5-C8cycloalkyl, phenyl, naphthyl, C7-C12aralkyl, halogen, C1-C8alkoxy or a -Y-Z group, R3 is hydrogen, C1-C8alkyl, a -Y-Z group or a -Y-O-Z' group, X is hydrogen or Li, Na, K, 1/2 Mg, 1/2 Ca, 1/2 Zn, 1/2 Co (II), 1/2 Cu (II), 1/2 Ni (II), 1/3 Cr (III), 1/3 Fe (III), wherein R4, R5, R6 and R7 are each independently of one another hydrogen, C1-C12alkyl, hydroxyethyl, cyclohexyl, phenyl or benzyl, Y is a direct bond or a divalent group of one of the following formulae:
-R8-, -R8-CONH-R9-, -R8-SO2-R9-, -R8-SO2NH-R9-, wherein R8, R9 and R10 are each independently of one another C1-C20alkylene which may be substituted by 1-10 hydroxyl groups or are C2-C2alkylene which is interrupted by 1-10 -O- or -NH-, and Z is a -SO3X group, and Z' is -SO3X, with the proviso that the compound of formula I contains at least one group of formula -SO3X.
wherein R1 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, -COO-R9-OSO3X or -R2 is hydrogen, OH, C1-C8alkyl, C5-C8cycloalkyl, phenyl, naphthyl, C7-C12aralkyl, halogen, C1-C8alkoxy or a -Y-Z group, R3 is hydrogen, C1-C8alkyl, a -Y-Z group or a -Y-O-Z' group, X is hydrogen or Li, Na, K, 1/2 Mg, 1/2 Ca, 1/2 Zn, 1/2 Co (II), 1/2 Cu (II), 1/2 Ni (II), 1/3 Cr (III), 1/3 Fe (III), wherein R4, R5, R6 and R7 are each independently of one another hydrogen, C1-C12alkyl, hydroxyethyl, cyclohexyl, phenyl or benzyl, Y is a direct bond or a divalent group of one of the following formulae:
-R8-, -R8-CONH-R9-, -R8-SO2-R9-, -R8-SO2NH-R9-, wherein R8, R9 and R10 are each independently of one another C1-C20alkylene which may be substituted by 1-10 hydroxyl groups or are C2-C2alkylene which is interrupted by 1-10 -O- or -NH-, and Z is a -SO3X group, and Z' is -SO3X, with the proviso that the compound of formula I contains at least one group of formula -SO3X.
2. An ink composition according to claim 1 comprising as component c) a compound of formula I, wherein R1 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, -COO-R9-OSO3X or -SO3X, R2 is hydrogen, C1-C8alkyl, C7-C8phenylalkyl or a -Y-Z group, R3 is hydrogen, C1-C4alkyl, -Y-Z group or a -Y-O-Z' group, X is hydrogen or Li, Na, K, wherein R4, R5, R6 and R7 are each independently of one another H, C1-C4alkyl or hydroxyethyl, Y is a direct bond or a group selected from -R8-, -R8-CONH-R9-, wherein R8 is C1-C6alkylene and R9 and R10 are each independently of the other C1-C10alkylene which may be substituted by 1 or 2 hydroxyl groups or C2-C20alkylene which is interrupted by 1-10 -O-, and Z is a -SO3X group and is Z' -SO3X.
3. An ink composition according to claim 2 comprising as component c) a compound of formula I, wherein R1 is hydrogen, chloro, ~CO~(OC2H4)x~OSO3X or -SO3X, R2 is hydrogen, C1-C8alkyl, C7-C9phenylalkyl or a -Y-Z group, R3 is hydrogen or a -Y-Z group and x is an integer from 2 to 8, and X, Y and Z are as defined in claim 2.
4. An ink composition according to claim 3 comprising as component c) a compound of formula I, wherein R1, R2 and R3 are as defined in claim 3, X is Li, Na, K or Y is a direct bond or a group selected from -R8-, -R8-CONH-R9- or Z is a -SO3X group, and R4, R5, R6, R7, R8 and R9 are as defined in claim 2.
5. An ink composition according to claim 1 comprising as component c) a compound of formula I, wherein R2 is in ortho-position and R3 is in para-position to the OH group.
6. An aqueous ink composition according to claim 1, comprising as component c) 0.1 to 10% by weight of at least one compound of formula I.
7. Use of an ink composition as claimed in claim 1 for ink jet printing.
8. A compound of formula I' wherein R1 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, -COO-R9-OSO3X or -SO3X, R2 is hydrogen, OH, C1-C8alkyl, C5-C6cycloalkyl, phenyl, naphthyl, C7-C12aralkyl, halogen, C1-C8alkoxy or a -Y-Z group, R3 is hydrogen, C1-C8alkyl, or a -Y-Z group, X is hydrogen or Li, Na, K, 1/2 Mg, 1/2 Ca, 1/2 Zn, 1/2 Co (II), 1/2 Cu (II), 1/2 Ni (II), 1/3 Cr (III), 1/3 Fe (III), wherein R4, R5, R6 and R7 are each independently of one another hydrogen, C1-C12alkyl, hydroxyethyl, cyclohexyl, phenyl or benzyl, Y is a group selected from:
-R8-, -R8-CONH-R9-, -R8-SO2-R9-, -R8-SO2NH-R9-, wherein R8, R9 and R10 are each independently of one another C1-C20alkylene which may be substituted by 1-10 hydroxyl groups or are C2-C20alkylene which is interrupted by 1-10 -O- or -NH-, and Z is a -SO3X group, with the proviso that the compound of formula I' contains at least one group of formula -SO3X.
-R8-, -R8-CONH-R9-, -R8-SO2-R9-, -R8-SO2NH-R9-, wherein R8, R9 and R10 are each independently of one another C1-C20alkylene which may be substituted by 1-10 hydroxyl groups or are C2-C20alkylene which is interrupted by 1-10 -O- or -NH-, and Z is a -SO3X group, with the proviso that the compound of formula I' contains at least one group of formula -SO3X.
9. A compound of the formula I' according to claim 8 which contains two -SO3X
groups.
groups.
10. A compound of formula I' according to claim 8, wherein R1 is hydrogen, chloro, ~CO~(OC2H4)x OSO3X or -SO3X, R2 is hydrogen, C1-C8alkyl, C7-C9phenylalkyl or a -Y-Z group, R3 is hydrogen or a -Y-Z group, X is Li, Na, K or x is an integer from 2 to 8, and Z is a -SO3X group, with the proviso that the compound of formula I' contains at least two groups of formula -SO3X.
11. A compound of the formula I' according to claim 8, wherein R 2 is in ortho-position and R3 is in para-position to the OH group.
12. Use of a compound of formula I as defined in claim 1 as light stabilizer for aqueous ink compositions.
13. A recording material based on paper or a plastic sheet which contains at least one compound of formula I according to claim 1.
14. A recording material based on paper or a plastic sheet according to claim 13, which is suitable for the ink jet printing process.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH308589 | 1989-08-25 | ||
| CH3085/89-7 | 1989-08-25 | ||
| CH14190 | 1990-01-17 | ||
| CH141/90-3 | 1990-01-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2023919A1 CA2023919A1 (en) | 1991-02-26 |
| CA2023919C true CA2023919C (en) | 2001-01-30 |
Family
ID=25683643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023919A Expired - Fee Related CA2023919C (en) | 1989-08-25 | 1990-08-23 | Light-stabilised ink compositions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5124723A (en) |
| EP (1) | EP0415880B1 (en) |
| JP (1) | JPH0391573A (en) |
| CA (1) | CA2023919C (en) |
| DE (1) | DE59008830D1 (en) |
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| US6008268A (en) | 1994-10-21 | 1999-12-28 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
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| US5849411A (en) | 1995-06-05 | 1998-12-15 | Kimberly-Clark Worldwide, Inc. | Polymer film, nonwoven web and fibers containing a photoreactor composition |
| ES2161357T3 (en) | 1995-06-28 | 2001-12-01 | Kimberly Clark Co | STABILIZING COLORING COMPOSITION. |
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| SK102397A3 (en) | 1995-11-28 | 1998-02-04 | Kimberly Clark Co | Colorant stabilizers |
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| DE69810001T2 (en) * | 1997-04-28 | 2003-04-17 | Seiko Epson Corp | Ink composition for producing a lightfast image |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| SK1542000A3 (en) | 1998-06-03 | 2001-11-06 | Kimberly Clark Co | Neonanoplasts produced by microemulsion technology and inks for ink jet printing |
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| US6228157B1 (en) | 1998-07-20 | 2001-05-08 | Ronald S. Nohr | Ink jet ink compositions |
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| DE60002294T2 (en) | 1999-01-19 | 2003-10-30 | Kimberly Clark Co | DYES, COLOR STABILIZERS, INK COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
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| US6508872B2 (en) * | 2001-02-26 | 2003-01-21 | Hewlett-Packard Company | Lightfast additive molecule for inkjet ink |
| US20050053734A1 (en) * | 2001-03-12 | 2005-03-10 | Hutter G. Frederick | Stabilizer-containing cationic colloidal dispersion polymers for ink jet coatings |
| US20050053736A1 (en) * | 2001-03-12 | 2005-03-10 | G. Frederick Hutter | Cationic colloidal dispersion polymers for ink jet coatings |
| US20020192438A1 (en) * | 2001-03-12 | 2002-12-19 | Westvaco Corporation | Stabilizer-containing cationic colloidal dispersion polymers for ink jet coatings |
| AU2001280902A1 (en) * | 2001-05-10 | 2003-12-22 | Lexmark International, Inc. | Ink compositions containing ultraviolet absorbers |
| AU2001279116A1 (en) * | 2001-08-01 | 2003-02-17 | Lexmark International, Inc. | Ink compositions containing ultraviolet absorbers |
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| US6572969B1 (en) | 2002-05-16 | 2003-06-03 | Meadwestvaco Corporation | Core shell polymeric compositions |
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| ATE316104T1 (en) | 2002-06-12 | 2006-02-15 | Meadwestvaco Corp Law Dept | CATIONIC CORE/SHELL PARTICLES WITH ACID-SWELLABLE SHELLS |
| KR100547109B1 (en) * | 2002-11-14 | 2006-01-26 | 삼성전자주식회사 | Functional additives having the UV-absorbing substituent and ink composition containing the same |
| US7141104B2 (en) * | 2003-06-05 | 2006-11-28 | Agfa-Gevaert | UV-absorbing ink composition for ink-jet printing |
| JP4936673B2 (en) * | 2005-02-10 | 2012-05-23 | 株式会社東芝 | Polymer electrolyte membrane and direct methanol fuel cell |
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|---|---|---|---|---|
| NL223154A (en) * | 1956-12-14 | |||
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| US3282886A (en) * | 1962-07-27 | 1966-11-01 | Du Pont | Polycarbonamides of improved photostability and dye lightfastness |
| FR2252341A1 (en) * | 1973-04-06 | 1975-06-20 | Ciba Geigy Ag | 2-(2-Hydroxyphenyl) benzotriazoles prodn - by reducing 1-oxides with hydrazine hydrate in high-boiling ether solvent |
| US4256493A (en) * | 1979-10-04 | 1981-03-17 | Dai Nippon Tokyo Co., Ltd. | Jet ink composition |
| JPS5774193A (en) * | 1980-10-28 | 1982-05-10 | Fuji Photo Film Co Ltd | Ink jet recording picture forming method |
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| EP0257151B1 (en) * | 1986-08-22 | 1992-01-29 | Chemipro Kasei Kaisha, Ltd. | Method for preparing 2-phenylbenzotriazoles and 2-phenylbenzotriazole-n-oxides |
| JPS6346277A (en) * | 1986-08-13 | 1988-02-27 | Canon Inc | Recording liquid |
| US4926190A (en) * | 1987-02-18 | 1990-05-15 | Ciba-Geigy Corporation | Ink jet recording process using certain benzotriazole derivatives as light stabilizers |
| GB8720365D0 (en) * | 1987-08-28 | 1987-10-07 | Sandoz Ltd | Organic compounds |
| EP0345212A1 (en) * | 1988-05-04 | 1989-12-06 | Ciba-Geigy Ag | Process to prevent yellowing of polyamide fibres finished with stain-proofing agents |
| US5096781A (en) * | 1988-12-19 | 1992-03-17 | Ciba-Geigy Corporation | Water-soluble compounds as light stabilizers |
| US4929250A (en) * | 1989-03-14 | 1990-05-29 | Ciba-Geigy Corporation | Ultraviolet absorbing lenses and method of making the same |
-
1990
- 1990-08-16 DE DE59008830T patent/DE59008830D1/en not_active Expired - Fee Related
- 1990-08-16 EP EP90810617A patent/EP0415880B1/en not_active Expired - Lifetime
- 1990-08-23 CA CA002023919A patent/CA2023919C/en not_active Expired - Fee Related
- 1990-08-27 JP JP2225022A patent/JPH0391573A/en active Pending
-
1991
- 1991-07-19 US US07/734,013 patent/US5124723A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2023919A1 (en) | 1991-02-26 |
| US5124723A (en) | 1992-06-23 |
| EP0415880B1 (en) | 1995-04-05 |
| EP0415880A3 (en) | 1991-07-24 |
| EP0415880A2 (en) | 1991-03-06 |
| JPH0391573A (en) | 1991-04-17 |
| DE59008830D1 (en) | 1995-05-11 |
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