CA2198867C - Water-resistant recording material for inkjet printing - Google Patents
Water-resistant recording material for inkjet printing Download PDFInfo
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- CA2198867C CA2198867C CA002198867A CA2198867A CA2198867C CA 2198867 C CA2198867 C CA 2198867C CA 002198867 A CA002198867 A CA 002198867A CA 2198867 A CA2198867 A CA 2198867A CA 2198867 C CA2198867 C CA 2198867C
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- water
- recording material
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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
- D21H19/00—Coated paper; Coating material
- D21H19/72—Coated paper characterised by the paper substrate
-
- 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
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
- D21H13/08—Synthetic cellulose fibres from regenerated cellulose
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/24—Polyesters
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- 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
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- 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
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
-
- 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
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
Abstract
Water-resistant recording material for the inkjet process using water-based inks, having a substrate paper which, in addition to cellulosic fibres, contains 1-40 % fibres and on one side or both sides of which a water- resistant recording layer is arranged. After storage for 24 hours at 23 ·C i n water, the recording material has over 80 % of the tear strength of the dry paper, measured according to DIN 53128. Even after the storage in water, the colour difference .DELTA.E, measured according to DIN 6174, of coloured area s of the primary colours applied in the inkjet process is less than 10, based on the initial colour values.
Description
~JVO 96/20091 PC~'1EP95104848 Water-resistant recording material for inkjet printing The invention relates to a water-resistant recording material for inkjet printing, which has the character of paper and extremely high water resistance of the printed image and of the substrate material for the recording layer.
DE-A-30 18 342 A describes,a synthetic paper for inkjet printing, which paper, after being printed on in the inkjet printer, is rendered transparent by means of 1.0 heat in order to obtain multicolour inkjet recordings having high recording density, good colour reproduction and high water resistance. The print which initially appears pale acquires high contrast and water resistance only as a result of subsequent melting. Papers of this 1.5 type then have the disadvantage of low opacity (high transparency) and that of the additional process step of the thermal aftertreatment.
DE-A-O1 64 196 A discloses a recording layer for inkjet processes on a sheet-like base material which also 20 includes papers of synthetic fibres, the layer containing both a cationic polymer and a polyvalent metal salt for fixing aqueous inks. In addition, water-penetrable or water-swellable binders, such as, for example, polyvinyl alcohol, and pigments, such as, for example, calcium 25 carbonate, kaolin and urea/formaldehyde fillers may be present in such a layer. Owing to the choice of the components used (PVA; polyvalent metal salt; cationic polymer), the water resistance of the prints in the inkjet process is relatively low even a.f the water 30 resistance test described (immersion for one minute in water followed by drying) is described as being positive.
The aim of this application was primarily to produce a rapidly drying and stackable (non-offsetting) paper having a brilliant print.
35 DE-A-43 30 428 describes an inkjet recording sheet on which recordings having good water resistance can be produced. This is achieved using a water-resistant substrate, which may be a glastic film or a synthetic paper. In addition to finely divided porous pigment, the recording layer necessarily contains, as the main component, amphoteric ion latex of s cationic colloid quality. DE-A-43 30 428 expressly states that, using conventional binders without this special synthetic polymer latex, the water resistance after printing is insufficient. Regarding the substrate material, it is stated that a synthetic paper of polypropylene, impregnated paper or plastic films are suitable.
1o JP-A-4-74685 relates generally to a recording material which can be printed on or written on in the moist state or on which copies can be produced in the wet state. The recording layer contains synthetic polymer latex, pigment, crosslinking agent and wax. The substrate material used is a material comprising cellulosic fibres and synthetic polymer fibres, so that the 15 substrate becomes thermoplastic only at 180°C or at higher temperatures.
For applications outdoors or in continuous contact with water, inkjet papers known to date are not suitable without further process steps, such as lamination with film, since the water resistance of the base papers and of the recording layer are not sufficient. It is precisely for applications 2 o such as, for examples, building plans, maps, site plans for example for divers, labels, sign plates and markings that inkjet prints which are mechanically stable and have unlimited colour stability even under the influence of water are required.
The present invention is directed towards the provision of a 2s recording material for inkjet printing, which.material is suitable for outdoor use, including underwater use, and resists any kind of influence by humidity or water. Both mechanical strength of the substrate paper under the influence of water and water resistance of the inkjet image are required for this purpose.
Furthermore, a brilliant, high-contrast, coloured or black inkjet print having 3 o high resolution and very crisp edges is required.
According to one aspect of the invention, that is provided water-resistant recording material for an inkjet process using water-based inks, the recording material comprising; a substrate paper containing from 10% by 2 °~ X67 - ~. a binder composed of a specific cationic copolymer and which may contain further different resinous binder. The substrate sheet may be a natural pulp paper, a polymeric film, synthetic pulp paper sheet, and synthetic fibre paper sheet.
For applications outdoors . or in continuous contact with water, inkjet papers known to date are not suitable without further process steps, such as lamina-tion with film, since the water resistance of the base papers and of the recording layer are not sufficient. It ' is precisely for applications such as, for example, building plans, maps, site plans, for example for divers, labels, sign plates and markings that inkj et prints which are mechanically stable and have unlimited colour stabil-ity even under the influence of water are required.
It is therefore the object of the present inven-tion to provide a recording material for inkjet printing, which material is suitable for outdoor use, including underwater use, and resists any kind of influence by humidity or water. Both mechanical strength of the substrate paper under the influence of water and water resistance of the inkjet image are~required for this purpose. Furthermore, a brilliant, high-contrast, coloured or black inkj et print having high resolution and very crisp edges is required.
According to the invention this object is achieved by a water-resistant recording material for the ink-jet pro-cess using water-based inks, having a substrate paper containing from lOX by weight to 90% by weight cellulosic fibres and from 1X by weight to 40X by weight of synthe-tic fibres and from 50% by weight to 5X by weight (all percentages are based on total weight of the substrate paper) of binder selected from polyvinyl acetate, polyvi-nyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile terpolymers, styrene/
(meth)acrylate copolymers, (meth)acrylic polymers, ethy-lene/(meth)acrylic acid copolymers and having a recording weight to 90% by weight of cellulosic fibers and from 40% by weight to 1 % by weight of synthetic fibers, the synthetic fibers selected from the group , consisting of polyamide fibers, polyester fibers, viscose fibers, and mixtures thereof; the substrate paper comprising from 50% by weight to 5% by weight of binder selected from the group consisting of polyvinyl acetate, polyvinyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile terpolymers, styrene/(meth) acrylate to copolymers, (meth)acrylic polymers and ethylene/(meth)acrylic acid copolymers, the binder excluding water soluble polymer binders; at least one recording layer arranged on at least one main surface of the substrate paper the recording layer having a basis weight of 10 g/m2 to 50 g/m2 and containing an abrasion-resistance pigment and a dried residue of an aqueous polymer dispersion as polymeric binder; the aqueous polymer dispersion having a minimum film formation temperature between -20°C and +50°C and, if desired, the recording layer further containing a water soluble binder selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives and a crosslinking agent for the binder; and the 2 o recording material after storage for 24 hours at 23°C in water having over 80% of a tear strength of the recording material before the storage in water, measured according to DIN 53128 and having a colour difference 0E of less than 10, measured according to DIN 6174, of areas of primary colours applied to the recording layer in an inkjet process, based on initial colour values 2 5 before the storage in water.
In addition to the binder or binder, the substrate paper preferably also contains fillers and/or pigments, the binder content being correspondingly reduced as a result of their presence. Suitable pigments are kaolin, barium sulphate, calcium carbonate, calcium sulphate and Ti02. The pigment filler 3 o content may be 2.0% by weight to 30% by weight based on the total weight of the substrate paper. The wet strength of the substrate paper can be tailored to the requirements by the concomitant use of crosslinking agents for the 3a binder and/or wet strength agents. The binders are selected polyvinyl acetate, polycinyl acetate copolymers, styrene/butadiene copolumers, s styrene/butadiene/ acrylonitrile terpolyers, styrene/(meth acrylate copolymers, (meth)-acrylic polymers, ethylene/(meth) acrylic acid copolymers.
Such film-forming polymers are commercially available.
For example, melamine/formaldehyde resins or urea/formaldehyde resins may be used as crosslinking WO 96/20091 ~ ~ ~ ~ ~ ~ ~ PCTIEP95/04848 agents. The substrate paper is produced on conventional paper machines by known processes and provided with the binder, preferably in the size press and/or by subsequent coating in a conventional coating machine. For example, polyamide fibres, polyester fibres, viscose fibres or mixtures thereof may be present as synthetic fibres in the substrate paper. The basis weight of the substrate paper may be 50 g/m~ to 300 g/mz, preferably 80 g/m~ to 200 g/m2.
Owing to the low absorptivity of the paper for water-based inks, direct printing by means of an inkjet printer gives a poorly drying and blurred image which is not water resistant. The substrate paper itself has excellent water resistance, which is manifested by a high tear strength in the completely wet state.
A water-resistant recording layer is therefore applied to one side or both sides of this paper. This said recording layer contains binder, pigment (s) , prefer ably dye fixing compositions, and further conventional auxiliaries.
Surprisingly. it was found that the combination of the special paper which contains synthetic fibres with coatings based on highly porous finely divided pigments leads to an abrasion-resistant and extremely water-resistant paper which, even, for example, after storage in water for 24 hours, retains its strength and shows the image information without abrasion, virtually without loss of contrast.
The recording layer applied to the synthetic base paper results in rapid ink absorption and in fixing of the dyes contained in the printing ink. Furthermore, this coating must have excellent adhesion to the base paper, both in the wet and in the dry state. The coating , itself must have high cohesion so that mechanical stress due to flexing, pleating, folding or rubbing, both in the , wet and in the dry state, does not damage the layer or the printed image.
In order to ensure good absorptivity for water-based inks, porous pigment, in particular silica, is preferably used in the recording layer. Suitable pigments have a surface area (measured according to BET) of over 200 m2/g.
Suitable pigments are, for example, precipitated silica particles having a mean particle size of between 1 ~cm and 20 5 ~,m, preferably between 4 ~.m and 12 Vim, and the abovementioned BET surface area.
Water-soluble, cationic polymers having a high content of quaternary ammonium groups and which became water insoluble upon drying of the recording layer are preferably present in the recording layer in order to fix the ink dyes.
Quaternary polyacrylates, polydiallyldimethylammonium chloride, canonically modified polystyrene, cationically modified starch, cationically modified polyvinyl alcohol, quaternary polyethyleneimine, quaternary polyvinylpyridine and copolymers of these compounds with one another or with other nonionic or anionic monomer units are suitable . 0 . 1 to 1 part of cationic polymer is preferably added per part of porous pigment.
In order to obtain a particularly water-resistant layer, it is expedient to choose for the pigment a binder which can no longer be superficially dissolved by water after the generally water-based coating has dried. Polymer dispersions, such as, for example, vinyl acetate homo- or copolymers, acrylate (co)polymers, styrene/butadiene copolymers, ethylene copolymers or vinyl chloride copolymers have proved suitable for this purpose. In order to ensure the flexibility of the layer and adhesion to the paper, dispersions having a minimum film formation temperature between -20°C and +50°C, preferably between -10°C and +20°C, are used. Water-soluble 30 binders, such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivatives, may additionally be used. In order further to increase the water resistance, crosslinking agents which react 5a during drying of the layer may be incorporated into the coating solution. Suitable substances are urea/formaldehyde or melamine/formaldehyde resins, aziridines, po]yfunctional isocyanates and boric acid (for PVA).
Optical brighteners, wetting agents, further pigments, for example aluminium hydroxides or aluminium WO 96/20091 ~ ~ ~ ~ ~ ~ PCT/EP95l04848 s oxides, kaolin, calcium carbonate, dyes, adhesion promo-ters, antifoams, thickeners, dispersants, etc., may~also be present as auxiliaries in the layer.
The ink absorption layer is applied to the r synthetic paper with the aid of conventional coating processes, for example by roller application and metering c by means of an air brush or rotating doctor blade, preferably from aqueous dispersion, and is dried by means of hot air. The coating weight of the dried coating is between 10 and 50 g/m2, preferably 15 to 30 g/m~. This coating weight is necessary in order to permit rapid absorption of the ink liquid into the coating during printing and thus to prevent blurring of the image lines.
The coating weight may be varied depending on the printer and amount of ink.
The ink absorption layer of the present invention exhibits excellent adhesion to the synthetic base paper and has good cohesion and flexibility, so that it with-stands any mechanical stresses both in the dry and in the wet state. The coating is thus resistant to flexing, folding and abrasion; furthermore, the layer cannot be damaged in the layer adhesion test by means of a self-adhesive tape, similar to the crosshatch test.
The coated paper has high resistance to mechani cal stress, i.e. initial tearing and complete tearing of the paper are possible only with the use of great force, both in the dry and in the wet state. In particular, in the completely wet state, the paper has over 80~ of the tear strength of the dry paper, measured according to DIN
53128.
The paper according to the present invention can, using commercial inkj et printers, be printed with a high-contrast image which has crisp edges and high resolution and may be coloured in the case of colour printers. The paper absorbs the generally water-based ink rapidly into , the coating and is dry and non-smudging shortly after printing. Suitable printers are, for example, printers which operate according to the bubblejet principle or piezoelectric principle, as are available in various ~JVO 96!20091 versions, for example from the companies Canon, Epson, Hewlett Packard, etc. Both small-format (DIN A3 and A4) and large-format prints, for example rolls for posters, are possible. The inks used in the abovementioned printers contain, as a rule, further auxiliaries, such as, for example, high boilers (glycols, NMP, etc.) and wetting agents, in addition to water and anionic dyes.
The water-soluble anionic dyes of these inks are fixed in the coating by ionic interaction with the cationic fixing agents so strongly that the printed image becomes extremely water-resistant. The printed image is also very resistant to flexing, pleating, folding and scratching, both in the wet and in the dry state, so that the image information has unlimited stability even under extreme environmental conditions. Inks which have high lightfastness even against W light are preferably chosen for image production. Owing to the fixing of the dyes and the water resistance of the coating itself, the material withstands the action of water even over long periods. Thus, the colour intensity (contrast) of the printed image decreases only slightly, if at all, during storage for 24 hours in water at 23C. In any case, the colour stability under these conditions is so good that, after this treatment, the colour difference OE of coloured areas of the primary colours black, cyan, magenta, yellow, blue, red and green is less than 10, based on the initial colour values.
Test methods:
Tear strength of the wet paper and resistance of the printed image A test image which contains in particular large ' coloured areas of all primary colours (cyan, magenta, yellow and black) and of the binary mixed colours (blue, green, red)' is applied to the water-resistant inkjet paper by means of an inkjet printer. 10 minutes after production of the test image, the recording sheet is ~1~~~67 immersed completely in water at 23 °C for 24 hours . After this storage time, the mechanical strength of the paper in the wet state in the longitudinal and transverse directions is determined according to DIN 53128 (tear strength). The tear strength of the dry paper condi-tioned at 23°C and 50~ relative humidity is also determined.
Furthermore, the paper stored in water for 24 hours is dried in a drying oven at 80°C for 5 minutes.
As was done directly after the test printing, the colour location, in Cielab coordinates, of each coloured area is then determined by means of a colorimeter according to DIN 6174. The colour difference DE, calculated from the measurements before and after storage of the particular coloured area in water, is a measure of the discoloration of the printed areas or fixing of the dyes of the inkjet inks.
Example 1 A commercial synthetic 140 g/m~ paper consisting of 61~ of cellulosic fibres, 4~ of synthetic fibres, 12~
of synthetic binders and auxiliaries is coated with the following coating composition with a coating weight (dry solids) of 25 g/ms by means of a rotating doctor blade and is dried in a drying oven at 100°C for 5 minutes.
- Water 600 g - Precipitated silica FFC 320 DS
(Degussa) 80 g - Poly(diallyldimethylammonium) chloride having an average molecular weight of 75,000 10 g - Vinyl chloride/vinyl acetate copolymer dispersion (505 solids content) 90 g - Wetting agent 2.5 g - Polyvinyl alcohol Mowiol 4/88 (Hoechst), .
10~ strength solution 225 g - Ammonia (25~ solids content) 7 g The coating composition has a solids content of 15.8 and a pH of 8Ø
~~VO 96!20091 PCTlEP95I04848 The paper coated in this manner is printed with a test print by means of a Canon BJC 800 inkjet printer with associated ink cartridges. It has extremely high water resistance: the image-bearing paper stored a.n water a for 24 hours at 23°C has a tear strength of 3.16 N
longitudinally and of 3.64 N transversely, compared with 1.6 N longitudinally and 2.0 N transversely in the dry state.
The coloured areas show only very little or no colour changes compared with the initial colour values as a result of the treatment:
OE
Black: 0.9 Cyan: 5.0 Magenta: 6.5 Yellow: 8.1 Blue: 1.3 Green: 2.1 Red: 4,~
, After this treatment, the print exhibits a high contrast, high-resolution image having crisp edges and shows no visible change.
DE-A-30 18 342 A describes,a synthetic paper for inkjet printing, which paper, after being printed on in the inkjet printer, is rendered transparent by means of 1.0 heat in order to obtain multicolour inkjet recordings having high recording density, good colour reproduction and high water resistance. The print which initially appears pale acquires high contrast and water resistance only as a result of subsequent melting. Papers of this 1.5 type then have the disadvantage of low opacity (high transparency) and that of the additional process step of the thermal aftertreatment.
DE-A-O1 64 196 A discloses a recording layer for inkjet processes on a sheet-like base material which also 20 includes papers of synthetic fibres, the layer containing both a cationic polymer and a polyvalent metal salt for fixing aqueous inks. In addition, water-penetrable or water-swellable binders, such as, for example, polyvinyl alcohol, and pigments, such as, for example, calcium 25 carbonate, kaolin and urea/formaldehyde fillers may be present in such a layer. Owing to the choice of the components used (PVA; polyvalent metal salt; cationic polymer), the water resistance of the prints in the inkjet process is relatively low even a.f the water 30 resistance test described (immersion for one minute in water followed by drying) is described as being positive.
The aim of this application was primarily to produce a rapidly drying and stackable (non-offsetting) paper having a brilliant print.
35 DE-A-43 30 428 describes an inkjet recording sheet on which recordings having good water resistance can be produced. This is achieved using a water-resistant substrate, which may be a glastic film or a synthetic paper. In addition to finely divided porous pigment, the recording layer necessarily contains, as the main component, amphoteric ion latex of s cationic colloid quality. DE-A-43 30 428 expressly states that, using conventional binders without this special synthetic polymer latex, the water resistance after printing is insufficient. Regarding the substrate material, it is stated that a synthetic paper of polypropylene, impregnated paper or plastic films are suitable.
1o JP-A-4-74685 relates generally to a recording material which can be printed on or written on in the moist state or on which copies can be produced in the wet state. The recording layer contains synthetic polymer latex, pigment, crosslinking agent and wax. The substrate material used is a material comprising cellulosic fibres and synthetic polymer fibres, so that the 15 substrate becomes thermoplastic only at 180°C or at higher temperatures.
For applications outdoors or in continuous contact with water, inkjet papers known to date are not suitable without further process steps, such as lamination with film, since the water resistance of the base papers and of the recording layer are not sufficient. It is precisely for applications 2 o such as, for examples, building plans, maps, site plans for example for divers, labels, sign plates and markings that inkjet prints which are mechanically stable and have unlimited colour stability even under the influence of water are required.
The present invention is directed towards the provision of a 2s recording material for inkjet printing, which.material is suitable for outdoor use, including underwater use, and resists any kind of influence by humidity or water. Both mechanical strength of the substrate paper under the influence of water and water resistance of the inkjet image are required for this purpose.
Furthermore, a brilliant, high-contrast, coloured or black inkjet print having 3 o high resolution and very crisp edges is required.
According to one aspect of the invention, that is provided water-resistant recording material for an inkjet process using water-based inks, the recording material comprising; a substrate paper containing from 10% by 2 °~ X67 - ~. a binder composed of a specific cationic copolymer and which may contain further different resinous binder. The substrate sheet may be a natural pulp paper, a polymeric film, synthetic pulp paper sheet, and synthetic fibre paper sheet.
For applications outdoors . or in continuous contact with water, inkjet papers known to date are not suitable without further process steps, such as lamina-tion with film, since the water resistance of the base papers and of the recording layer are not sufficient. It ' is precisely for applications such as, for example, building plans, maps, site plans, for example for divers, labels, sign plates and markings that inkj et prints which are mechanically stable and have unlimited colour stabil-ity even under the influence of water are required.
It is therefore the object of the present inven-tion to provide a recording material for inkjet printing, which material is suitable for outdoor use, including underwater use, and resists any kind of influence by humidity or water. Both mechanical strength of the substrate paper under the influence of water and water resistance of the inkjet image are~required for this purpose. Furthermore, a brilliant, high-contrast, coloured or black inkj et print having high resolution and very crisp edges is required.
According to the invention this object is achieved by a water-resistant recording material for the ink-jet pro-cess using water-based inks, having a substrate paper containing from lOX by weight to 90% by weight cellulosic fibres and from 1X by weight to 40X by weight of synthe-tic fibres and from 50% by weight to 5X by weight (all percentages are based on total weight of the substrate paper) of binder selected from polyvinyl acetate, polyvi-nyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile terpolymers, styrene/
(meth)acrylate copolymers, (meth)acrylic polymers, ethy-lene/(meth)acrylic acid copolymers and having a recording weight to 90% by weight of cellulosic fibers and from 40% by weight to 1 % by weight of synthetic fibers, the synthetic fibers selected from the group , consisting of polyamide fibers, polyester fibers, viscose fibers, and mixtures thereof; the substrate paper comprising from 50% by weight to 5% by weight of binder selected from the group consisting of polyvinyl acetate, polyvinyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile terpolymers, styrene/(meth) acrylate to copolymers, (meth)acrylic polymers and ethylene/(meth)acrylic acid copolymers, the binder excluding water soluble polymer binders; at least one recording layer arranged on at least one main surface of the substrate paper the recording layer having a basis weight of 10 g/m2 to 50 g/m2 and containing an abrasion-resistance pigment and a dried residue of an aqueous polymer dispersion as polymeric binder; the aqueous polymer dispersion having a minimum film formation temperature between -20°C and +50°C and, if desired, the recording layer further containing a water soluble binder selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives and a crosslinking agent for the binder; and the 2 o recording material after storage for 24 hours at 23°C in water having over 80% of a tear strength of the recording material before the storage in water, measured according to DIN 53128 and having a colour difference 0E of less than 10, measured according to DIN 6174, of areas of primary colours applied to the recording layer in an inkjet process, based on initial colour values 2 5 before the storage in water.
In addition to the binder or binder, the substrate paper preferably also contains fillers and/or pigments, the binder content being correspondingly reduced as a result of their presence. Suitable pigments are kaolin, barium sulphate, calcium carbonate, calcium sulphate and Ti02. The pigment filler 3 o content may be 2.0% by weight to 30% by weight based on the total weight of the substrate paper. The wet strength of the substrate paper can be tailored to the requirements by the concomitant use of crosslinking agents for the 3a binder and/or wet strength agents. The binders are selected polyvinyl acetate, polycinyl acetate copolymers, styrene/butadiene copolumers, s styrene/butadiene/ acrylonitrile terpolyers, styrene/(meth acrylate copolymers, (meth)-acrylic polymers, ethylene/(meth) acrylic acid copolymers.
Such film-forming polymers are commercially available.
For example, melamine/formaldehyde resins or urea/formaldehyde resins may be used as crosslinking WO 96/20091 ~ ~ ~ ~ ~ ~ ~ PCTIEP95/04848 agents. The substrate paper is produced on conventional paper machines by known processes and provided with the binder, preferably in the size press and/or by subsequent coating in a conventional coating machine. For example, polyamide fibres, polyester fibres, viscose fibres or mixtures thereof may be present as synthetic fibres in the substrate paper. The basis weight of the substrate paper may be 50 g/m~ to 300 g/mz, preferably 80 g/m~ to 200 g/m2.
Owing to the low absorptivity of the paper for water-based inks, direct printing by means of an inkjet printer gives a poorly drying and blurred image which is not water resistant. The substrate paper itself has excellent water resistance, which is manifested by a high tear strength in the completely wet state.
A water-resistant recording layer is therefore applied to one side or both sides of this paper. This said recording layer contains binder, pigment (s) , prefer ably dye fixing compositions, and further conventional auxiliaries.
Surprisingly. it was found that the combination of the special paper which contains synthetic fibres with coatings based on highly porous finely divided pigments leads to an abrasion-resistant and extremely water-resistant paper which, even, for example, after storage in water for 24 hours, retains its strength and shows the image information without abrasion, virtually without loss of contrast.
The recording layer applied to the synthetic base paper results in rapid ink absorption and in fixing of the dyes contained in the printing ink. Furthermore, this coating must have excellent adhesion to the base paper, both in the wet and in the dry state. The coating , itself must have high cohesion so that mechanical stress due to flexing, pleating, folding or rubbing, both in the , wet and in the dry state, does not damage the layer or the printed image.
In order to ensure good absorptivity for water-based inks, porous pigment, in particular silica, is preferably used in the recording layer. Suitable pigments have a surface area (measured according to BET) of over 200 m2/g.
Suitable pigments are, for example, precipitated silica particles having a mean particle size of between 1 ~cm and 20 5 ~,m, preferably between 4 ~.m and 12 Vim, and the abovementioned BET surface area.
Water-soluble, cationic polymers having a high content of quaternary ammonium groups and which became water insoluble upon drying of the recording layer are preferably present in the recording layer in order to fix the ink dyes.
Quaternary polyacrylates, polydiallyldimethylammonium chloride, canonically modified polystyrene, cationically modified starch, cationically modified polyvinyl alcohol, quaternary polyethyleneimine, quaternary polyvinylpyridine and copolymers of these compounds with one another or with other nonionic or anionic monomer units are suitable . 0 . 1 to 1 part of cationic polymer is preferably added per part of porous pigment.
In order to obtain a particularly water-resistant layer, it is expedient to choose for the pigment a binder which can no longer be superficially dissolved by water after the generally water-based coating has dried. Polymer dispersions, such as, for example, vinyl acetate homo- or copolymers, acrylate (co)polymers, styrene/butadiene copolymers, ethylene copolymers or vinyl chloride copolymers have proved suitable for this purpose. In order to ensure the flexibility of the layer and adhesion to the paper, dispersions having a minimum film formation temperature between -20°C and +50°C, preferably between -10°C and +20°C, are used. Water-soluble 30 binders, such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivatives, may additionally be used. In order further to increase the water resistance, crosslinking agents which react 5a during drying of the layer may be incorporated into the coating solution. Suitable substances are urea/formaldehyde or melamine/formaldehyde resins, aziridines, po]yfunctional isocyanates and boric acid (for PVA).
Optical brighteners, wetting agents, further pigments, for example aluminium hydroxides or aluminium WO 96/20091 ~ ~ ~ ~ ~ ~ PCT/EP95l04848 s oxides, kaolin, calcium carbonate, dyes, adhesion promo-ters, antifoams, thickeners, dispersants, etc., may~also be present as auxiliaries in the layer.
The ink absorption layer is applied to the r synthetic paper with the aid of conventional coating processes, for example by roller application and metering c by means of an air brush or rotating doctor blade, preferably from aqueous dispersion, and is dried by means of hot air. The coating weight of the dried coating is between 10 and 50 g/m2, preferably 15 to 30 g/m~. This coating weight is necessary in order to permit rapid absorption of the ink liquid into the coating during printing and thus to prevent blurring of the image lines.
The coating weight may be varied depending on the printer and amount of ink.
The ink absorption layer of the present invention exhibits excellent adhesion to the synthetic base paper and has good cohesion and flexibility, so that it with-stands any mechanical stresses both in the dry and in the wet state. The coating is thus resistant to flexing, folding and abrasion; furthermore, the layer cannot be damaged in the layer adhesion test by means of a self-adhesive tape, similar to the crosshatch test.
The coated paper has high resistance to mechani cal stress, i.e. initial tearing and complete tearing of the paper are possible only with the use of great force, both in the dry and in the wet state. In particular, in the completely wet state, the paper has over 80~ of the tear strength of the dry paper, measured according to DIN
53128.
The paper according to the present invention can, using commercial inkj et printers, be printed with a high-contrast image which has crisp edges and high resolution and may be coloured in the case of colour printers. The paper absorbs the generally water-based ink rapidly into , the coating and is dry and non-smudging shortly after printing. Suitable printers are, for example, printers which operate according to the bubblejet principle or piezoelectric principle, as are available in various ~JVO 96!20091 versions, for example from the companies Canon, Epson, Hewlett Packard, etc. Both small-format (DIN A3 and A4) and large-format prints, for example rolls for posters, are possible. The inks used in the abovementioned printers contain, as a rule, further auxiliaries, such as, for example, high boilers (glycols, NMP, etc.) and wetting agents, in addition to water and anionic dyes.
The water-soluble anionic dyes of these inks are fixed in the coating by ionic interaction with the cationic fixing agents so strongly that the printed image becomes extremely water-resistant. The printed image is also very resistant to flexing, pleating, folding and scratching, both in the wet and in the dry state, so that the image information has unlimited stability even under extreme environmental conditions. Inks which have high lightfastness even against W light are preferably chosen for image production. Owing to the fixing of the dyes and the water resistance of the coating itself, the material withstands the action of water even over long periods. Thus, the colour intensity (contrast) of the printed image decreases only slightly, if at all, during storage for 24 hours in water at 23C. In any case, the colour stability under these conditions is so good that, after this treatment, the colour difference OE of coloured areas of the primary colours black, cyan, magenta, yellow, blue, red and green is less than 10, based on the initial colour values.
Test methods:
Tear strength of the wet paper and resistance of the printed image A test image which contains in particular large ' coloured areas of all primary colours (cyan, magenta, yellow and black) and of the binary mixed colours (blue, green, red)' is applied to the water-resistant inkjet paper by means of an inkjet printer. 10 minutes after production of the test image, the recording sheet is ~1~~~67 immersed completely in water at 23 °C for 24 hours . After this storage time, the mechanical strength of the paper in the wet state in the longitudinal and transverse directions is determined according to DIN 53128 (tear strength). The tear strength of the dry paper condi-tioned at 23°C and 50~ relative humidity is also determined.
Furthermore, the paper stored in water for 24 hours is dried in a drying oven at 80°C for 5 minutes.
As was done directly after the test printing, the colour location, in Cielab coordinates, of each coloured area is then determined by means of a colorimeter according to DIN 6174. The colour difference DE, calculated from the measurements before and after storage of the particular coloured area in water, is a measure of the discoloration of the printed areas or fixing of the dyes of the inkjet inks.
Example 1 A commercial synthetic 140 g/m~ paper consisting of 61~ of cellulosic fibres, 4~ of synthetic fibres, 12~
of synthetic binders and auxiliaries is coated with the following coating composition with a coating weight (dry solids) of 25 g/ms by means of a rotating doctor blade and is dried in a drying oven at 100°C for 5 minutes.
- Water 600 g - Precipitated silica FFC 320 DS
(Degussa) 80 g - Poly(diallyldimethylammonium) chloride having an average molecular weight of 75,000 10 g - Vinyl chloride/vinyl acetate copolymer dispersion (505 solids content) 90 g - Wetting agent 2.5 g - Polyvinyl alcohol Mowiol 4/88 (Hoechst), .
10~ strength solution 225 g - Ammonia (25~ solids content) 7 g The coating composition has a solids content of 15.8 and a pH of 8Ø
~~VO 96!20091 PCTlEP95I04848 The paper coated in this manner is printed with a test print by means of a Canon BJC 800 inkjet printer with associated ink cartridges. It has extremely high water resistance: the image-bearing paper stored a.n water a for 24 hours at 23°C has a tear strength of 3.16 N
longitudinally and of 3.64 N transversely, compared with 1.6 N longitudinally and 2.0 N transversely in the dry state.
The coloured areas show only very little or no colour changes compared with the initial colour values as a result of the treatment:
OE
Black: 0.9 Cyan: 5.0 Magenta: 6.5 Yellow: 8.1 Blue: 1.3 Green: 2.1 Red: 4,~
, After this treatment, the print exhibits a high contrast, high-resolution image having crisp edges and shows no visible change.
Claims (12)
PROPERYT OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Water-resistant recording material for an inkjet process using water-based inks, said recording material comprising:
a substrate paper containing from 10% by weight to 90% by weight of cellulosic fibers and from 40% by weight to 1% by weight of synthetic fibers, said synthetic fibers selected from the group consisting of polyamide fibers, polyester fibers, viscose fibers, and mixtures thereof, said substrate paper comprising from 50% by weight to 5% by weight of binder selected from the group consisting of polyvinyl acetate, polyvinyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile terpolymers, styrene/(meth) acrylate copolymers, (meth)acrylic polymers and ethylene/(meth)acrylic acid copolymers, said binder excluding water soluble polymer binders;
at least one recording layer arranged on at least one main surface of the substrate paper said recording layer having a basis weight of 10g/m2 to 50g/m2 and containing an abrasion-resistance pigment and a dried residue of an aqueous polymer dispersion as polymeric binder;
said aqueous polymer dispersion having a minimum film formation temperature between -20°C and +50°C and, if desired, said recording layer further containing a water soluble binder selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives and a crosslinking agent for the binder; and said recording material after storage for 24 hours at 23°C in water having over 80% of a tear strength of said recording material before said storage in water, measured according to DIN 53128 and having a colour difference .DELTA.E of less than 10, measured according to DIN 6174, of areas of primary colours applied to the recording layer in an inkjet process, based on initial colour values before said storage in water.
a substrate paper containing from 10% by weight to 90% by weight of cellulosic fibers and from 40% by weight to 1% by weight of synthetic fibers, said synthetic fibers selected from the group consisting of polyamide fibers, polyester fibers, viscose fibers, and mixtures thereof, said substrate paper comprising from 50% by weight to 5% by weight of binder selected from the group consisting of polyvinyl acetate, polyvinyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile terpolymers, styrene/(meth) acrylate copolymers, (meth)acrylic polymers and ethylene/(meth)acrylic acid copolymers, said binder excluding water soluble polymer binders;
at least one recording layer arranged on at least one main surface of the substrate paper said recording layer having a basis weight of 10g/m2 to 50g/m2 and containing an abrasion-resistance pigment and a dried residue of an aqueous polymer dispersion as polymeric binder;
said aqueous polymer dispersion having a minimum film formation temperature between -20°C and +50°C and, if desired, said recording layer further containing a water soluble binder selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives and a crosslinking agent for the binder; and said recording material after storage for 24 hours at 23°C in water having over 80% of a tear strength of said recording material before said storage in water, measured according to DIN 53128 and having a colour difference .DELTA.E of less than 10, measured according to DIN 6174, of areas of primary colours applied to the recording layer in an inkjet process, based on initial colour values before said storage in water.
2. The water-resistant recording material of claim 1, wherein the recording layer contains silica as the abrasion-resistant pigment, the silica comprising 10% by weight to 70% by weight, of the total recording layer weight.
3. The water resistant recording material of claim 2, wherein the polymer in said aqueous polymer dispersion having a minimum film formation temperature from -20°C to +50°C is selected from the group consisting of polyvinyl acetate, polyvinyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile teropolymers, styrene/(meth)acrylate copolymers, (meth)acrylic polymers, ethylene/(meth)acrylic acid copolymers, ethylene copolymers or vinyl chloride copolymers, vinyl chloride copolymers and mixtures thereof.
4. The water-resistance recording material according to claims 2, wherein the recording material includes a recording ink containing water-soluble dyes.
5. The water resistant recording material according to claim 3, wherein the recording material includes a recording ink containing water-soluble dyes.
6. The water resistant recording material of claim 1, wherein the polymer in said aqueous polymer dispersion having a minimum film formation temperature from -20°C to + 50°C is selected from the group consisting of polyvinyl acetate, polyvinyl acetate copolymers, styrene/butadiene copolymers, styrene/butadiene/acrylonitrile teropolymers, styrene/(meth)acrylate copolymers, (meth)acrylic polymers, ethylene/(meth)acrylic acid copolymers, ethylene copolymers or vinyl chloride copolymers, vinyl chloride copolymers and mixtures thereof.
7. The water-resistant recording material according to claim 6, wherein the recording material includes a recording ink containing water-soluble dyes.
8. The water-resistant recording material of claim 1, wherein the recording layer further contains a polymeric cationic fixing agent for aqueous inks.
9. The water-resistant recording material of claim 8, wherein the polymeric cationic fixing agent is selected from the group consisting of modified polystyrene, a cationic (meth)acrylate copolymers, a quaternary polyimine, poly (diallyldimethylammonium) chloride and a mixture thereof.
10. The water-resistant recording material according to claim 9, wherein the recording material includes a recording ink containing water-soluble dyes.
11. The water-resistant recording material according to claim 8, wherein the recording material includes a recording ink containing water-soluble dyes.
12. The water-resistant recording material according to claim 1, wherein the recording material includes a recording ink containing water-soluble dyes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4446551.3 | 1994-12-24 | ||
| DE4446551A DE4446551C1 (en) | 1994-12-24 | 1994-12-24 | Water-resistant recording material for ink-jet printing |
| PCT/EP1995/004848 WO1996020091A1 (en) | 1994-12-24 | 1995-12-08 | Water-resistant recording material for inkjet printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2198867A1 CA2198867A1 (en) | 1996-07-04 |
| CA2198867C true CA2198867C (en) | 2002-09-10 |
Family
ID=6537084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002198867A Expired - Fee Related CA2198867C (en) | 1994-12-24 | 1995-12-08 | Water-resistant recording material for inkjet printing |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5853540A (en) |
| EP (1) | EP0799136B1 (en) |
| JP (1) | JPH11500367A (en) |
| AT (1) | ATE168632T1 (en) |
| CA (1) | CA2198867C (en) |
| DE (2) | DE4446551C1 (en) |
| WO (1) | WO1996020091A1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19628342C2 (en) * | 1996-07-13 | 1999-03-04 | Sihl Gmbh | Recording material and its use for inkjet printing |
| DE19709735A1 (en) * | 1997-03-10 | 1998-09-17 | Sihl Gmbh | Inkjet recording material |
| WO1999054145A1 (en) * | 1998-04-21 | 1999-10-28 | Mitsubishi Paper Mills Limited | Ink jet recording paper |
| US6818685B1 (en) | 1998-07-09 | 2004-11-16 | W. R. Grace & Co. -Conn. | Ink-receptive coatings and recording medium prepared therefrom |
| ATE261820T1 (en) * | 1998-07-09 | 2004-04-15 | Grace W R & Co | INK RECEPTION LAYERS AND A RECORDING MEDIUM CONTAINING THEM |
| GB2352681A (en) | 1999-08-04 | 2001-02-07 | Ilford Imaging Uk Ltd | Ink jet printing method |
| US6414065B1 (en) * | 1999-11-05 | 2002-07-02 | Celanese International Corporation | Multifunctional poly(vinyl alcohol) binder for fine particle size calcium carbonate pigment |
| GB2356374A (en) * | 1999-11-18 | 2001-05-23 | Ilford Imaging Uk Ltd | Printing process |
| US20010024713A1 (en) * | 2000-02-22 | 2001-09-27 | Dirk Quintens | Ink jet recording material |
| US20020012774A1 (en) * | 2000-05-19 | 2002-01-31 | Neithardt William A. | Water-based, water resistant ink jet media |
| GB2372871A (en) * | 2001-02-09 | 2002-09-04 | Roy O'hara | Water resistant and tear resistant map |
| MXPA04001306A (en) * | 2001-08-17 | 2004-05-20 | Avery Dennison Corp | Topcoat compositions, substrates containing a topcoat derived therefrom, and methods of preparing the same. |
| ATE393802T1 (en) | 2001-12-19 | 2008-05-15 | Clariant Finance Bvi Ltd | USE OF DYES FOR INKJET PRINTING MATERIALS |
| GB0130316D0 (en) | 2001-12-19 | 2002-02-06 | Clariant Int Ltd | Composition for printing recording materials |
| US20030137571A1 (en) * | 2002-01-23 | 2003-07-24 | Horst Friedel | Recording element for ink jet printing |
| GB0208444D0 (en) | 2002-04-12 | 2002-05-22 | Clariant Int Ltd | Composition for printing recording materials |
| JP3969255B2 (en) * | 2002-09-10 | 2007-09-05 | コニカミノルタホールディングス株式会社 | Inkjet recording paper for water-based dye ink |
| MXPA05004562A (en) * | 2002-11-13 | 2005-07-26 | Clariant Finance Bvi Ltd | Mono azo dyes. |
| EP1598205B8 (en) * | 2003-02-07 | 2007-10-17 | Mitsui Chemicals, Inc. | Ink-jet recording sheet |
| JP2004243603A (en) * | 2003-02-13 | 2004-09-02 | Mitsubishi Paper Mills Ltd | Inkjet recording sheet |
| IT1397619B1 (en) * | 2009-10-22 | 2013-01-18 | Gruppo Cordenons Spa | PAPER MATERIAL WITH SYNTHETIC FIBERS AND RELATIVE MANUFACTURING METHOD |
| JP5869593B2 (en) * | 2011-03-29 | 2016-02-24 | ヒューレット−パッカード デベロップメント カンパニー エル．ピー．Ｈｅｗｌｅｔｔ‐Ｐａｃｋａｒｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ， Ｌ．Ｐ． | Inkjet media |
| US8496784B2 (en) | 2011-04-05 | 2013-07-30 | P.H. Glatfelter Company | Process for making a stiffened paper |
| US9133583B2 (en) | 2011-04-05 | 2015-09-15 | P.H. Glatfelter Company | Process for making a stiffened paper |
| EP3738782A1 (en) * | 2019-05-16 | 2020-11-18 | Sihl GmbH | Inkjet printed film for decorative applications |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4092457A (en) * | 1973-03-24 | 1978-05-30 | Kanzaki Paper Manufacturing Co., Ltd. | Method for the production of a synthetic fiber paper having an improved printability for offset printing and the product thereof |
| US4517244A (en) * | 1981-08-06 | 1985-05-14 | Canon Kabushiki Kaisha | Recording medium and ink jet recording paper |
| US4636805A (en) * | 1984-03-23 | 1987-01-13 | Canon Kabushiki Kaisha | Record-bearing member and ink-jet recording method by use thereof |
| JPH0753469B2 (en) * | 1987-12-29 | 1995-06-07 | 新王子製紙株式会社 | Inkjet recording sheet and manufacturing method thereof |
| DE68916173T2 (en) * | 1988-11-02 | 1994-11-10 | Canon Kk | Ink jet recording system and recording method using the same. |
| US5213873A (en) * | 1989-10-20 | 1993-05-25 | Oji Paper Co., Ltd. | Aqueous ink-jet recording sheet |
| JP2729698B2 (en) * | 1990-07-18 | 1998-03-18 | ダイニック株式会社 | Recording sheet |
| US5270103A (en) * | 1990-11-21 | 1993-12-14 | Xerox Corporation | Coated receiver sheets |
| JP3213630B2 (en) * | 1991-07-25 | 2001-10-02 | 三菱製紙株式会社 | Inkjet recording sheet |
| US5541633A (en) * | 1992-02-12 | 1996-07-30 | Xerox Corporation | Ink jet printing of concealed images on carbonless paper |
| US5478631A (en) * | 1992-09-09 | 1995-12-26 | Kanzaki Paper Mfg. Co., Ltd. | Ink jet recording sheet |
-
1994
- 1994-12-24 DE DE4446551A patent/DE4446551C1/en not_active Expired - Fee Related
-
1995
- 1995-12-08 US US08/836,376 patent/US5853540A/en not_active Expired - Fee Related
- 1995-12-08 JP JP8520145A patent/JPH11500367A/en active Pending
- 1995-12-08 CA CA002198867A patent/CA2198867C/en not_active Expired - Fee Related
- 1995-12-08 EP EP95942084A patent/EP0799136B1/en not_active Expired - Lifetime
- 1995-12-08 WO PCT/EP1995/004848 patent/WO1996020091A1/en active IP Right Grant
- 1995-12-08 AT AT95942084T patent/ATE168632T1/en not_active IP Right Cessation
- 1995-12-08 DE DE69503664T patent/DE69503664T2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0799136A1 (en) | 1997-10-08 |
| WO1996020091A1 (en) | 1996-07-04 |
| ATE168632T1 (en) | 1998-08-15 |
| DE69503664D1 (en) | 1998-08-27 |
| US5853540A (en) | 1998-12-29 |
| CA2198867A1 (en) | 1996-07-04 |
| JPH11500367A (en) | 1999-01-12 |
| DE4446551C1 (en) | 1996-03-14 |
| DE69503664T2 (en) | 1998-12-24 |
| EP0799136B1 (en) | 1998-07-22 |
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