WO1999064248A1 - Papier d'enregistrement par jet d'encre - Google Patents
Papier d'enregistrement par jet d'encre Download PDFInfo
- Publication number
- WO1999064248A1 WO1999064248A1 PCT/JP1999/003073 JP9903073W WO9964248A1 WO 1999064248 A1 WO1999064248 A1 WO 1999064248A1 JP 9903073 W JP9903073 W JP 9903073W WO 9964248 A1 WO9964248 A1 WO 9964248A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fine particles
- absorbing layer
- group
- ink
- formula
- Prior art date
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Classifications
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- 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
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- 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
- B41M5/506—Intermediate layers
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- 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
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- 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
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
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- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- the present invention relates to an ink jet recording paper, and more particularly to an ink jet recording paper in which bleeding of an image after printing is improved.
- Ink jet recording is a method of recording images and characters by flying micro droplets of ink by various operating principles and attaching them to a recording sheet such as paper.Relatively high speed, low noise, and multicolor printing It has advantages such as easy conversion. With regard to nozzle clogging and maintenance, which has been a problem in the past, improvements have been made from both the ink and equipment aspects. Current, it is rapidly being applied to various fields, such as various types of printers, facsimile machines, and computer terminals. Widespread.
- the recording paper used in this ink jet recording method has a high print dot density, a bright and vivid color tone, and ink is quickly absorbed and prints out even if the print dot power is too high. It is required that the spread of the printing dots in the horizontal direction should not be unnecessarily large, and that the force and surrounding area should be smooth and not blurred. Especially when the ink absorption speed is low, when two or more color ink droplets are printed in an overlapping manner, the droplets may cause a repelling phenomenon on the recording paper to become uneven, or a boundary region of a different color. in order to easily greatly reduced the quality of the image blurred the color of each other, mosquito? is necessary is to ensure that to have a high ink absorption properties as a record paper.
- a large number of techniques have been conventionally proposed.
- Recording papers containing fine particles such as colloidal silica, and recording papers containing fine particles of alumina hydrate described in JP-A-5-16517 are known. ing.
- a porous recording paper using inorganic fine particles and a hydrophilic binder and having minute voids formed in the ink absorbing layer can obtain relatively high gloss.
- fine-particle silica having an anionic surface As such inorganic fine particles because excellent gloss can be obtained, and in particular, the average particle size of primary particles synthesized by a gas phase method is preferably used.
- Composite particles having an average particle diameter of 100 nm or less, which are obtained by combining a fine particle silica having a particle diameter of 30 nm or less and a cationic polymer, are particularly preferable in terms of achieving both glossiness and high porosity.
- Japanese Unexamined Patent Publication No. 57-36692 discloses the use of a basic mordant latex.
- Japanese Unexamined Patent Publication No. 59-1988 discloses a method for impregnating polyethyleneimine.
- No. 62-17474184 describes the use of polyallylamine as a mordant.
- Japanese Patent Application Laid-Open Nos. 6-234268, 7-124411 and others disclose a number of techniques for improving the fixability of an ink dye by adding a cationic mordant. .
- the present inventors have found that blurring of an image after printing is improved at a specific pH of a structure of a force-thione polymer and a coating film, and reached the present invention.
- an ink jet recording paper having a porous ink absorbing layer containing inorganic fine particles and a hydrophilic binder has a high glossiness and a high ink absorption capacity while maintaining high gloss and high ink absorption capacity.
- An object of the present invention is to provide an ink jet recording paper with improved image bleeding. Disclosure of the invention
- the ink jet recording paper of the present invention will be described.
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 1, R 2 and R 3 each represent an alkyl group
- J represents a divalent linking group.
- X— represents an anion group.
- Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group. Q includes the case where two or more monomers are copolymerized.
- X 4 0 to 1 0 0 mol%
- y is 0 to 6 0 mol 0/0.
- Fine particles with an average particle size of 200 nm or less formed by including a hydrophilic binder, inorganic fine particles with an average primary particle size of 30 nm or less on a support, and fine particles of the formula (1).
- An ink jet recording paper which has an ink absorbing layer containing a water-soluble cationic polymer and has a film surface pH of 3 to 6.5.
- Equation (1) +0 ⁇
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 1, R 2 and R 3 each represent an alkyl group
- J represents a divalent linking group
- X— represents an anion group
- Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group.
- Q includes the case where two or more monomers are copolymerized.
- X is 40 to 100 mol%, and y is 0 to 60 mol 0 / o.
- An ink jet recording sheet having an ink absorbing layer containing a water-soluble cationic polymer having an average molecular weight of 100,000 or less, wherein the film surface pH of the ink absorbing layer is 3 to 6.
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 1, R 2 and R 3 each represent an alkyl group
- J represents a divalent linking group
- X represents an anion group
- Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group, c
- Q includes the case where two or more monomers are copolymerized.
- X 5 0 to 1 0 0 mol%, y is from 0 to 5 0 mol 0/0.
- An ink absorbing layer containing a hydrophilic binder, inorganic fine particles having an average primary particle diameter of 30 nm or less, and a water-soluble cationic polymer represented by the formula (1) is provided on the support.
- an ink jet recording paper wherein the film surface pH of the ink absorbing layer is 3 to 6.5.
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 2 and R 3 each represent an alkyl group
- J represents a divalent linking group
- X represents an anion group
- Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group
- Q includes the case where two or more monomers are copolymerized.
- X is 40 to 100 mol%, and y is 0 to 60 mol 0 / o. 5.
- a hydrophilic binder On a support, a hydrophilic binder, inorganic fine particles having an average primary particle size of 30 nm or less, and a water-soluble cationic polymer having an average molecular weight of 100,000 or less represented by the formula (1) are provided.
- An ink-jet recording sheet having an ink-absorbing layer containing cationic composite particles, wherein the film surface pH of the ink-absorbing layer is 3 to 6.
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 1, R 2 and R 3 each represent an alkyl group
- J represents a divalent linking group
- X represents an anion group
- Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group.
- Q includes the case where two or more monomers are copolymerized.
- X 5 0 to 1 0 0 mol%, y is from 0 to 5 0 mol 0/0.
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 1, R 2 and R 3 each represent an alkyl group
- J represents a divalent linking group
- X represents an anion group
- Q represents a repeating unit derived from a monomer having an ethylenic unsaturated group
- c Q includes the case where two or more monomers are copolymerized.
- X is 40 to 100 mol%
- y is 0 to 60 mol%.
- the ink absorbing layer is a void type ink absorbing layer containing at least a hydrophilic binder and inorganic fine particles. It is considered that, by forming a film of fine particles containing inorganic fine particles together with a hydrophilic binder, the ink force is absorbed by voids formed between the fine particles.
- inorganic fine particles include light calcium carbonate, heavy carbonated calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, nordium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, and high.
- These inorganic fine particles preferably have an average primary particle size of 30 nm or less, and from the viewpoint that the effects of the present invention can be more remarkably obtained, the average primary particle size is 16 nm or less. Is more preferable.
- the lower limit of the average particle diameter of the primary particles is approximately 4 nm.
- silica or quasi-boehmite force is preferable from the viewpoint that the film has high transparency and fine voids can be formed, and in particular, a silicide force synthesized by a gas phase method is most preferably used.
- AEROSIL series manufactured by Nippon AEROSIL CO., LTD. Is commercially available as the fine particles formed by a gas phase method. These inorganic fine particles may be used as primary particles, or may be used in a state where secondary aggregated particles are formed.
- the fine particles finally observed on the recording paper may be those described in the claims of the present application.
- the “fine particles” include the above-mentioned inorganic fine particles, and preferably have an average particle diameter of 200 nm or less.
- the average particle diameter of the fine particles is determined by observing the recording paper with an electron microscope, determining the particle diameter of 100 arbitrary particles, and calculating the simple average value (number average).
- each particle size is represented by the diameter assuming a circle equal to the projected area
- the recording paper of the present invention has a force that includes at least the inorganic fine particles and a water-soluble cationic polymer described below.
- the inorganic fine particles are represented by the general formula (1).
- An embodiment in which cationic composite particles are formed and used together with the cationic polymer to be used is also preferably mentioned.
- the average particle size of the fine particles is preferably 200 nm or less, but if it is 160 nm or less, it is preferable in that the effects of the present invention can be more remarkably obtained. Les ,. From the viewpoint of achieving the effects of the present invention, the lower limit of the average particle size is not limited. For example, if the fine particles are formed using the inorganic fine particles having the above-mentioned average primary particle size, approximately 20 nm That is all.
- the ink absorbing layer of the ink jet recording paper contains at least a hydrophilic ink, fine particles having a specific particle size, and a cationic polymer represented by the formula (1).
- the inorganic fine particles form fine particles that are cationic composite particles together with a cationic polymer represented by the formula (1) having an average molecular weight of 100,000 or less. Used.
- the fine particles which are the composite particles are obtained by mixing the cationic polymer and the inorganic fine particles. can get.
- an aqueous solution containing a water-soluble cationic polymer is mixed with a dispersion containing inorganic fine particles having an anionic surface, agglomerates are generated.
- a dispersion treatment is applied to the mixed solution. Done.
- a dispersion liquid of inorganic fine particles converted into cations can be obtained.
- Various dispersers such as a high-speed rotating disperser, a medium stirring disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a colloid mill disperser, a roll mill disperser, and a high-pressure disperser are used as the dispersing method. You can do it.
- an ultrasonic disperser or a high-pressure disperser is preferably used from the viewpoint of efficiently dispersing the formed massive fine particles.
- Ultrasonic dispersers usually disperse energy by applying ultrasonic waves at 20 to 25 KHz, causing energy to nest in the solid-liquid interface, and are very efficiently dispersed. It is particularly useful when preparing relatively small amounts of dispersion.
- High-pressure dispersers are equipped with one or two homogenous valves at the outlet of a high-pressure pump with three or five pistons, whose clearance can be adjusted by screw or hydraulic pressure, The flow of the liquid medium sent by the high-pressure pump is restricted by the homogeneous valve and pressure is applied. At the moment when the liquid medium passes through the homogeneous valve, minute aggregates are crushed.
- Pressure applied to the homogenous valve is generally a to 5 0 1 0 0 OK g Z cm 2 , variance as possible out also be carried out also repeated many times be dispensed in a single pass.
- the above dispersion can be used in combination of two or more kinds.
- additives can be used for the preparation of fine particles which are cationic composite particles.
- a water-miscible organic solvent is preferable because the formation of fine lumps when the inorganic fine particles and the cationic polymer are mixed is suppressed.
- a water-miscible organic solvent is used in an amount of 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight in the dispersion.
- the type of inorganic fine particles used can vary widely depending on the type of cationic polymer, various additives, etc., but in general, the pH of the ionic cationic fine particle dispersion is 1 to 8, especially 2 to 7 Is preferred.
- the cationic polymer used in the present invention is represented by the formula (1).
- R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
- R ,, R 2 and R 3 preferably represent each an alkyl group is a methyl group or E Chi le group.
- Each of the alkyl groups may have a substituent.
- J represents a divalent linking group and represents a mere bond or a divalent organic group, and preferably represents a CON (R ′) — group (R ′ is a hydrogen atom or a substituted Represents an alkyl group which may have a group).
- X represents an anion group (halogen ion, methyl sulfate ion, p-toluenesulfonic acid ion, etc.).
- Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group.
- the 0 monomer include, for example, styrene, butadiene, and methyl methacrylate.
- Q includes the case where two or more monomers are copolymerized.
- X 4 0 to 1 0 0 mole 0/0
- y is 0 to 6 0 mole 0/0, preferably X is 5 0 to 1 0 0 mole 0 / o, y to the 0 5 0 mole 0 / 0, X is 7 0 to 1 0 0 mole 0/0, y is 0 to 3 0 mol 0/0 are particularly preferred.
- composition of the cationic polymer represented by the formula (1) are shown.
- the cationic polymer represented by the formula (1) preferably has an average molecular weight of 100,000 or less. This indicates a number average molecular weight.
- the number average molecular weight is a value converted into a polystyrene value obtained from gel permeation chromatography.
- the average molecular weight is 100,000 or less, it is possible to sufficiently suppress the generation of aggregates when an aqueous solution of the cationic polymer is added to a dispersion containing inorganic fine particles having an anionic surface. A liquid is easily obtained.
- the dispersion containing such a cationic polymer and inorganic fine particles is used for glossy paper for ink jet, higher gloss can be obtained. More preferably, it is 50,000 or less.
- the lower limit of the average molecular weight is generally at least 200 from the viewpoint of the water resistance of the dye, and is particularly preferably at least 500.
- the weight ratio between the inorganic fine particles and the cationic polymer can vary depending on the type and particle size of the inorganic fine particles, or the type and average molecular weight of the cationic polymer. Generally, 1: 0.01 or 1: 1 is preferable.
- Various hydrophilic binders can be used for the recording paper of the present invention. Hydrophilic binder mosquito? Preferably les, which do not exhibit a cohesive and significant ⁇ work upon mixed with inorganic fine particles and cationic polymer according to the present invention.
- hydrophilic binder examples include gelatin (preferably acid-treated gelatin), polyvinylpyridone (preferably having an average molecular weight of about 200,000 or more), pullulan, polyvinyl alcohol or a derivative thereof, and polyethylene glycol ( The average molecular weight is preferably 100,000 or more.), Hydroxyethyl cellulose, dextran, dextrin, and water-soluble polyvinyl butyral.
- gelatin preferably acid-treated gelatin
- polyvinylpyridone preferably having an average molecular weight of about 200,000 or more
- pullulan polyvinyl alcohol or a derivative thereof
- polyethylene glycol The average molecular weight is preferably 100,000 or more.
- Hydroxyethyl cellulose dextran, dextrin, and water-soluble polyvinyl butyral.
- hydrophilic binders are polyvinyl alcohol or cationically modified polyvinyl alcohol.
- the polyvinyl alcohol preferably used in the present invention has an average degree of polymerization of from 300 to 450, and is preferably used.
- the film having an average molecular weight of 100 or more has good brittleness. It is preferable because of its existence.
- the saponification degree of polyvinyl alcohol is preferably from 70 to 100%, particularly preferably from 80 to 100%.
- the cation-modified polyvinyl alcohol is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
- Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl-1- (2-acrylamide-1,2-dimethylethyl) ammonium chloride, trimethyl-1- (3-acrylamide 3,3-dimethyl).
- Propyl) ammonium chloride N-vinylimidazole, N-vinyl-1-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxyethyltrimethylammonium chloride , Trimethyl mono (3-methacrylamide propyl) ammonium ⁇ muclide, N- (1,1-dimethyl-13-dimethylaminopropyl) acrylamide, and the like.
- the ratio of cation-modified group containing monomers of cation-modified polyvinyl alcohol is 0 for vinyl acetate. 1 to 1 0 mol 0/0, preferably from 0. 2 to 5 mol 0/0.
- the degree of polymerization of cationically modified polyvinyl alcohol is usually 5 0 0 to 4 0 0 0, preferred properly 1 0 0 0 to 4 0 0 0 Ca? Preferred.
- the saponification degree of the cation-modified polyvinyl alcohol is usually 6 0 to 1 0 0 molar 0/0, preferably to 7 0 9 9 mol 0/0.
- the above-mentioned hydrophilic binder is used in a relatively small amount with respect to the inorganic fine particles so that the ink absorption layer becomes the ink absorption layer, and is used as little as possible as long as the film is formed stably and the adhesion to the support can be sufficiently maintained. It is preferred to use.
- the amount of the hydrophilic binder is generally about 1 to 3 to 110, and especially about 14 to 1 to 8 by weight relative to the inorganic fine particles.
- the hydrophilic binder is preferably hardened with a hardener in order to obtain high gloss and high ink absorption capacity without deteriorating the brittleness of the film.
- the hardener is generally a compound having a group capable of reacting with the hydrophilic binder, or a compound which promotes a mutual reaction between different groups of the hydrophilic binder. It is appropriately selected according to the situation.
- the hardener examples include epoxy hardeners (diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-diglycidyl cyclo).
- polyvinyl alcohol and / or cation-modified polyvinyl alcohol as the hydrophilic binder, it is preferable to use boric acid and its salts, and epoxy hardeners.
- boric acid and its salts.
- boric acid or a salt thereof are oxyacids and salts thereof having a boron atom as a central atom, and specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octanoic acid and their salts. Salt.
- the amount of the hardener type of hydrophilic binders, types of hardeners, the force varies by a ratio or the like with respect to types and a hydrophilic binder of the inorganic fine particles f, generally hydrophilic binder 1 g per 5 to 5 0 0 mg, preferably 10 to 400 mg.
- the hardener may be added to the coating liquid for forming the ink absorbing layer and / or the coating liquid for forming another layer adjacent to the ink absorbing layer when the coating liquid forming the ink absorbing layer is applied, or A coating liquid for forming the ink absorbing layer is applied to a support on which a coating liquid containing a hardening agent is applied in advance, or a coating liquid containing no hardening agent for forming an ink absorbing layer.
- the coating solution for forming the ink absorbing layer or the coating solution for forming the ink absorbing layer is preferably used because of the ability to supply the hardening agent to the ink absorbing layer by, for example, overcoating the coating agent solution, It is preferable to add a hardening agent to the coating solution of the layer adjacent to this and to supply the hardening agent at the same time as forming the ink absorbing layer.
- Various additives other than those described above can be added to the ink absorbing layer and other layers provided as needed of the ink jet recording paper of the present invention.
- JP-A-57-74192, JP-A-57-87989, JP-A-60-72785, JP-A-61-146591, JP-A-1-95091 and JP-A-3-13376 Discoloration preventing agents described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-121966.
- No. PH adjusters such as fluorescent brighteners, sulfuric acid, phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, defoamers, preservatives, thickeners, antistatic agents, matting agents And various other known additives.
- the volume of the voids in the ink-absorbing layer of the ink jet recording paper of the present invention (which is almost equal to the ink-absorbing capacity) is about 20 to 50 m 1 Zm 2 , and the porosity in this layer is about 0.5. Or 0.8.
- the ink absorbing layer described above may be composed of two or more layers, and in this case, the constitutions of the ink absorbing layers may be the same or different.
- the cationic polymer represented by the formula (1) can be added to all or some of the layers of the ink absorbing layer. It is preferable that at least the compound is added to the ink absorbing layer farthest from the support.
- a polymer other than the cationic polymer represented by the formula (1) can be used in combination for each ink absorption iRi.
- the cationic polymer other than the cationic polymer represented by the formula (1), which can be used in combination is arbitrarily selected from cationic polymers known in the related art for ink jet recording paper.
- cationic polymers known in the related art for ink jet recording paper capable to be possible
- Particularly preferred are those having a number average molecular weight of 1,000 to 100,000.
- the ratio of cationic monomer is 1 0 mole 0/0 or more preferably having a quaternary Anmoniumu bases, more preferably 2 0 mol% or more, particularly preferably 3 0 mol is 0/0 or more.
- the monomer having a quaternary ammonium base may be a single monomer or two or more monomers.
- the ink absorbing layer of the recording paper of the present invention needs to have a film surface pH of 3 to 6.5.
- the film surface pH is less than 3, even if the cationic polymer represented by the formula (1) is used, the effect of improving bleeding after printing is not obtained, and the porosity in the layer is also reduced, so that the ink absorption capacity is reduced. Decrease. Also, when the film surface pH exceeds 6.5, bleeding after printing is improved. It is not good, and the gloss decreases.
- Particularly preferred film surface pH is 3.6 to 5.3.
- the film surface pH of the ink absorbing layer can be measured by dropping 20 to 50 ⁇ l of deionized water onto the surface of the recording paper and using a commercially available surface pH electrode.
- the support for the ink jet recording paper may be a paper support, a plastic support, or a composite support used as a recording paper for an ink jet. It is preferable to use a hydrophobic support in which the ink does not penetrate.
- a transparent or opaque plastic resin film support As the hydrophobic support, a transparent or opaque plastic resin film support, a paper support having a paper surface laminated with polyethylene, and the like are preferably used.
- the transparent support include materials such as polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, cellophane, and celluloid. Film, etc., among which films having a property of resisting radiant heat when used as ⁇ are preferred, and polyethylene terephthalate is particularly preferred.
- the thickness of such a transparent support is preferably about 10 to 200 m. It forces an undercoat layer on the ink absorptive layer side and back layer side of the transparent support?, From the viewpoint of contact adhesiveness of the ink absorbing layer and the back layer and the support.
- Examples of the support used when it is not necessary to be transparent include resin-coated paper (so-called RC paper) having a polyolefin resin-coated layer to which a white pigment or the like is added on at least one of the base paper, polyethylene terephthalate, and the like.
- RC paper resin-coated paper
- a so-called white pet obtained by adding a white pigment to the rate is preferred.
- the support Prior to the application of the ink absorbing layer, the support is preferably subjected to a corona discharge treatment or a subbing treatment for the purpose of increasing the adhesive strength between the support and the ink absorbing layer.
- the recording sheet of the present invention does not necessarily need to be colorless, and may be a colored recording sheet.
- the ink jet recording paper of the present invention it is particularly preferable to use a paper support in which both sides of the base paper support are laminated with polyethylene, since the recorded image is close to photographic quality, and a high quality image can be obtained at low cost.
- a paper support laminated with polyethylene is described below.
- the base paper used for the paper support is made of wood pulp as a main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester in addition to wood pulp.
- synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester in addition to wood pulp.
- any of LBKP, LBS P, NBK P, NB SP, LDP, NDP, LUKP, NUKP can be used, but LB KP, NBS P, LB SP, NDP, LDP, which has a large amount of short fibers, can be used. It is preferable to use many.
- a chemical pulp containing less impurities sulfate pulp or sulfite pulp
- Base paper contains sizing agents such as higher fatty acids, alkyl ketene dimer, etc., white pigments such as calcium carbonate, talc, titanium oxide, paper strength agents such as starch, polyacrylamide, and polyvinyl alcohol, and fluorescent whitening.
- Agents, water retention agents such as polyethylene glycols, dispersants, and softening agents such as quaternary ammonium can be added as appropriate.
- the freeness of pulp used for papermaking is 200 to 500 ml according to the CSF standard.
- the sum of the 24 mesh residual weight% and the 42 mesh residual weight% specified in JIS-P-8207 is 30 to 70%. . Na us, it is preferred that the 4 mesh weight 0/0 of the residue is 20 wt% or less.
- the basis weight of base paper is 2502 Ca? Preferably 30 to, it is preferable in particular 50 to 200 g No.
- the thickness of the base paper is preferably 40 to 250 m.
- the base paper may be calendered at the papermaking stage or after papermaking to provide high smoothness.
- the base paper density is generally 0.7 to 1.2 gZm 2 (JIS—P—8 118). Further, the stiffness of the base paper is preferably 20 to 200 g under the conditions specified in JIS-P-8143.
- a surface sizing agent may be applied to the surface of the base paper.
- the surface sizing agent the same sizing agent as can be added to the base paper can be used.
- the pH of the base paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS-P-81 13.
- the polyethylene that covers the front and back of the base paper is mainly low-density polyethylene (L DP.E) and Z or high-density polyethylene (HD PE) .
- L DP.E low-density polyethylene
- HD PE high-density polyethylene
- Other LLDPE and polypropylene can also be used. .
- the polyethylene layer on the ink absorbing layer side is preferably a layer obtained by adding rutile or anatase type titanium oxide to polyethylene to improve opacity and whiteness as widely used in photographic printing paper.
- the titanium oxide content is generally between 3 and 20% by weight, preferably between 4 and 13% by weight, based on polyethylene.
- Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melt-extruded onto the base paper surface and coated, a so-called patterning process is applied to the matte surface, which can be obtained with ordinary photographic printing paper. Those having an eye surface can also be used in the present invention.
- the amount of polyethylene used on the front and back of the base paper depends on the ink absorption layer, the back layer, and the power selected to optimize the curl in low and high humidity. 2 0 to 4 0 m, the back layer side is 1 0 to 3 0 c further the polyethylene coated paper support is a m is Shi preferred to have the following characteristics les. 1. Tensile strength:? JI SP-8 1 1 3 to the longitudinal direction of 2 to an intensity defined by 3 0 Kg, it forces the transverse direction is 2 0 Kg from 1 preferred.
- the tear strength is preferably 10 to 200 g in the vertical direction and 20 to 200 g in the horizontal direction according to the method specified by JIS-P-81 16.
- Opacity Linear light incidence
- the transmittance of visible light under the measurement conditions of diffuse light transmission conditions is preferably 20% or less, particularly preferably 15% or less.
- a method for applying various hydrophilic layers, which are appropriately provided as needed, such as an ink absorbing layer and an undercoat layer, on the support of the recording paper of the present invention may be appropriately selected.
- the coating solution for forming each layer is applied on a support and dried.
- two or more layers can be applied simultaneously, and in particular, all the hydrophilic binder-containing layers need only be applied once, and simultaneous application is preferable.
- a mouth coating method As a coating method, a mouth coating method, a rod bar coating method, a dry coating method, a spray coating method, a curtain coating method, or a hopper described in US Patent No. 2,681,294.
- the extrusion coating method used is preferably used.
- a water-based ink is preferably used.
- the aqueous ink contains a colorant, a liquid medium containing water as a main component, and other additives.
- a coloring agent a water-soluble dye or a water-dispersible pigment such as a direct dye, an acid dye, a basic dye, a reactive dye, or a food dye used in ink jet recording can be used.
- the solvent for the aqueous ink examples include water and various water-soluble organic solvents, for example, alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol; dimethylformamide, dimethylacetamide, and the like.
- alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol
- dimethylformamide, dimethylacetamide, and the like Amides; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, and butylene.
- Glycol triethylen glycol, 1, 2, 6 —hexanetriol, thioglycol, hexylene glycol, diethylene glycol, glycerin, triethanolamine, etc.
- polyhydric alcohols such as diethylene glycol and triethanolamine / glycerin
- lower alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether
- water-based ink additives include, for example, pH regulators, sequestering agents, anti-binders, viscosity modifiers, surface tension regulators, wetting agents, surfactants, and water-proofing agents. .
- the aqueous ink liquid should have a surface tension at 20 in the range of 25 to 60 dyn Z cm, preferably 30 to 50 dyn Z cm, in order to have good wettability to the recording paper. preferable.
- the mixture was dispersed with a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd. under the conditions of 500 KgZcm 2 to obtain a uniform and almost transparent dispersion B1.
- Dispersion B 1 650 ml Fluorescent brightener dispersion (below) 20 ml titanium oxide dispersion (below) 25 ml polyvinyl alcohol (Kuraray PVA 203) 10% aqueous solution 5 ml polyvinyl alcohol (Kuraray PVA 235) 5 % Aqueous solution 270ml latex dispersion (AE 803 manufactured by Showa Kogyo Kogyo Co., Ltd.) 20ml pure water (total volume of 1000ml)
- Coating solution for second layer (amount per liter of coating solution)
- Dispersion B 1 650ml Optical brightener dispersion (below) 30ml Polyvinyl alcohol (Kuraray PVA 203) 10% aqueous solution 5ml Polyvinyl alcohol (Kuraray PVA 235) 5% aqueous solution 2 70 ml Latex dispersion (Showa Polymer AE 803) 20ml pure water Finish to 1 000ml)
- Coating solution for the third layer (Amount per liter of coating solution)
- Dispersion B 1 620 ml Fluorescent brightener dispersion (see below) 20 ml polyvinyl alcohol (Kuraray PVA 203) 10% aqueous solution 5 ml polyvinyl alcohol (Kuraray PVA 235) 5% aqueous solution 2 70 ml Latex dispersion Liquid (Showa Kogaku Kogyo AE 803) 10 ml pure water (to make the total volume 1 000 ml)
- Coating solution for 4th layer (Amount per liter of coating solution)
- Dispersion B 1 600 ml polyvinyl alcohol (Kuraray PVA 203) 10% aqueous solution 5 ml polyvinyl alcohol (Kuraray PVA 235) 5% aqueous solution 2 70 ml surfactant (saponin) 10% aqueous solution 10 ml Silicone dispersion (Toray 'Dow Corning' Silicone Co., Ltd., BY—22—83 9)) 20 ml pure water (to make the total volume 1 000 ml)
- Fluorescent brightener dispersion 100 ml of 3% acid-treated gelatin aqueous solution (containing 4 g of saponin and 2 g of cationic polymer P-9) contained an oil-soluble fluorescent brightener manufactured by Ciba-Geigy Corporation ( (UV I TEX-OB) A solution prepared by heating and dissolving 0.6 g and 12 g of diisodecyl phthalate in 25 ml of ethyl acetate was added, and the mixture was emulsified and dispersed with an ultrasonic homogenizer, and the whole amount was purified with pure water to 140 ml. To finish. Titanium oxide dispersion: A dispersion containing 40% by weight of titanium oxide (W10) manufactured by Ishihara Sangyo
- the viscosity of each of the above coating solutions was 30 to 40 cp at 40, and 10,000 to 20,000 at 15.
- polyethylene 2 thickness 240 6 weight polyethylene layer having a thickness of about 35 ⁇ M the recording surface 0 / 0 ANATA one peptidase type containing titanium dioxide, the backside poly ethylene layer having a thickness of about 30 m
- Each layer was applied to the first layer (5 Oyum), the second layer (50 m), the third layer (50yum), and the fourth layer (50 m) in this order. And this indicates the wet film thickness of each, and the first to fourth layers were applied simultaneously.
- Each coating solution was applied using a 4-layer slide hopper at 4 Ot: and cooled immediately after coating in a cooling zone maintained at 0, followed by air blowing at 20 to 30 for 60 seconds and 45 seconds.
- the recording paper 11 of the present invention was obtained by successively drying with a wind of 60 seconds and with a wind of 50 for 60 seconds.
- the resulting recording paper was then stored at 35 C for 2 days.
- the cationic polymer was changed as shown in Table 1 to prepare dispersions B2 to B10 in the same manner as the dispersion B1, and using this, the recording paper 1 10 was made in the same manner as recording paper 11.
- the value of the number average molecular weight of the cationic polymer is a value in terms of polystyrene obtained from gel permeation chromatography.
- the particle diameter of the fine particles contained in the ink absorbing layer of the recording paper 1 was measured with an electron microscope, and was found to be 60 nm.
- Dispersion B1 Same as Dispersion B1, except that in Preparation of Dispersion B1 used in Recording Paper-1 of Example 1, the pH of Solutions A1 and C1 was changed using nitric acid or aqueous sodium hydroxide solution, respectively. Then, Bl (f) was prepared from the dispersion B 1 (a), and recording papers 11 (a) to 1 (f) were prepared in the same manner as the recording paper 11 in the same manner as in the recording paper 11. Evaluation was performed in the same manner as in Example 1, and the results shown in Table 2 were obtained. In addition, the ink absorption rate was measured with a Bristow tester manufactured by Kumagai Riki Kogyo Co., Ltd., and the transfer amount after a contact time of 2 seconds was determined as the ink absorption capacity. Table 2 shows the results.
- dispersions B12 to B17 with the following changes added were prepared in the same manner as the dispersion B1, and the recording paper was prepared in the same manner as the recording paper 1. 1 2 to 17 were created.
- Dispersion B 12 Same as Dispersion B 1, except that the amount of cationic polymer was reduced to 2-3
- Dispersion B 13 Same as Dispersion B 1 except that the silica particles were changed to vapor phase silica (A200, manufactured by Nippon Aerosil Co., Ltd.) with an average primary particle size of 0.012
- B 14 Same as dispersion B 1 except that the silica particles were changed to gas phase method silica (OX50, manufactured by Nippon Aerological Co., Ltd.) with an average primary particle size of 0.04 m
- Dispersion B 15 Silica particles were used in the dispersion B 1 to obtain a primary particle having an average particle diameter of 0.007 ⁇ m in a gas phase method and an average particle diameter of the primary particles used in the dispersion B 13 of 0.01. Same as Dispersion B 1 except that the mixture was changed to a 1: 1 weight ratio mixture of fumed silica 2
- Dispersion B 16 Gas-phase method Siri force with average particle size of 0.007 ⁇ m primary particles used in dispersion B 1 and average particles of primary particles used in dispersion B 13 Same as Dispersion B 1 except that the mixture was changed to a 4: 1 weight ratio mixture of fumed silica with a diameter of 0.04 m
- Dispersion B 17 The average particle size of the primary particles used in the dispersion B 1 was 0.1%. The average particle diameter of the primary particles used in the gas phase method silicic acid of 0.7 ⁇ m and the dispersion B 14 is 0.0
- Dispersion B 1 Same as Dispersion B 1 except that the mixture was changed to a 1: 1 weight ratio of the gas phase method Siri force of 4.
- the particle size of the inorganic fine particles contained in the ink absorbing layer of each recording paper was measured with an electron microscope, and the results shown in Table 3 were obtained. Also, when the film surface pH of each recording paper was measured, the recording papers 12 to 17 were almost the same as the film surface pH of the recording paper 1 and were all pH 4.
- the procedure for preparing the first layer coating solution and the second layer coating solution was the same as that for preparing the first layer coating solution and the second layer coating solution, except that silica dispersion B 650 ml was used instead of silica dispersion Bl 65 Om 1.
- a recording paper (membrane surface pH 4.62) was prepared in the same manner as for recording paper 1 except that a liquid and a coating liquid for the second layer were prepared and used.
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99923974A EP1002660B1 (en) | 1998-06-10 | 1999-06-09 | Ink-jet recording paper |
JP52598899A JP3694896B2 (ja) | 1998-06-10 | 1999-06-09 | インクジェット記録用紙 |
DE69932991T DE69932991T2 (de) | 1998-06-10 | 1999-06-09 | Tintenstrahlaufzeichnungspapier |
US09/423,335 US6503604B1 (en) | 1998-06-10 | 1999-06-09 | Ink jet recording sheet |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17812698 | 1998-06-10 | ||
JP10/178126 | 1998-06-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999064248A1 true WO1999064248A1 (fr) | 1999-12-16 |
Family
ID=16043119
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/003073 WO1999064248A1 (fr) | 1998-06-10 | 1999-06-09 | Papier d'enregistrement par jet d'encre |
Country Status (5)
Country | Link |
---|---|
US (1) | US6503604B1 (ja) |
EP (1) | EP1002660B1 (ja) |
JP (1) | JP3694896B2 (ja) |
DE (1) | DE69932991T2 (ja) |
WO (1) | WO1999064248A1 (ja) |
Cited By (4)
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US6620470B2 (en) | 2000-08-31 | 2003-09-16 | Konica Corporation | Ink jet recording media |
EP1612054A1 (en) | 2004-07-02 | 2006-01-04 | Fuji Photo Film Co., Ltd. | Inkjet recording medium |
EP1655142A1 (en) | 2004-10-12 | 2006-05-10 | Mitsubishi Paper Mills Limited | Ink-jet recording material and method for preparing the same |
EP2106923A1 (en) | 2008-03-31 | 2009-10-07 | FUJIFILM Corporation | Inkjet recording medium and method of producing the same |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10101309B4 (de) * | 2000-01-14 | 2004-11-18 | Mitsubishi Paper Mills Limited | Tintenstrahl-Aufzeichnungsmaterial |
EP1211088A3 (en) * | 2000-11-29 | 2004-05-06 | Konica Corporation | Ink-jet recording sheet, ink-jet recording method and preparing method of ink-jet sheet |
US6846526B2 (en) | 2001-01-26 | 2005-01-25 | Eastman Kodak Company | Ink jet recording element |
US6543891B1 (en) | 2001-01-26 | 2003-04-08 | Eastman Kodak Company | Ink jet printing method |
DE60201357T2 (de) * | 2001-01-26 | 2005-11-10 | Eastman Kodak Co. | Tintenstrahlaufzeichnungselement und Druckverfahren |
US6619797B2 (en) | 2001-01-26 | 2003-09-16 | Eastman Kodak Company | Ink jet printing method |
US6423398B1 (en) * | 2001-01-26 | 2002-07-23 | Eastman Kodak Company | Ink jet printing method |
US6527387B2 (en) | 2001-01-26 | 2003-03-04 | Eastman Kodak Company | Ink jet printing method |
US6548151B2 (en) | 2001-01-26 | 2003-04-15 | Eastman Kodak Company | Ink jet recording element |
US6630212B2 (en) | 2001-01-26 | 2003-10-07 | Eastman Kodak Company | Ink jet recording element |
US6419355B1 (en) | 2001-01-26 | 2002-07-16 | Eastman Kodak Company | Ink jet printing method |
EP1226970B1 (en) * | 2001-01-26 | 2004-04-07 | Eastman Kodak Company | Ink jet recording element and printing method |
EP1226962B1 (en) | 2001-01-26 | 2007-11-28 | Eastman Kodak Company | Ink jet recording element and printing method |
EP1238815A3 (en) * | 2001-03-06 | 2003-11-19 | Eastman Kodak Company | Ink jet recording element and printing method |
US20030194539A1 (en) * | 2001-08-08 | 2003-10-16 | Hidenobu Ohya | Ink-jet recording medium and ink-jet image forming method using the recording medium |
US6815020B2 (en) | 2001-08-31 | 2004-11-09 | Eastman Kodak Company | Ink jet recording element |
US6689430B2 (en) | 2001-08-31 | 2004-02-10 | Eastman Kodak Company | Ink jet recording element |
US6447110B1 (en) | 2001-08-31 | 2002-09-10 | Eastman Kodak Company | Ink jet printing method |
EP1288012B1 (en) | 2001-08-31 | 2006-03-22 | Eastman Kodak Company | Ink jet recording element and printing method |
US6431701B1 (en) | 2001-08-31 | 2002-08-13 | Eastman Kodak Company | Ink jet printing method |
US6770336B2 (en) | 2001-12-12 | 2004-08-03 | Eastman Kodak Company | Ink jet recording element |
US6527388B1 (en) | 2001-12-12 | 2003-03-04 | Eastman Kodak Company | Ink jet printing method |
EP1319518B1 (en) | 2001-12-12 | 2007-01-17 | Eastman Kodak Company | Ink jet recording element and printing method |
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1999
- 1999-06-09 WO PCT/JP1999/003073 patent/WO1999064248A1/ja active IP Right Grant
- 1999-06-09 JP JP52598899A patent/JP3694896B2/ja not_active Expired - Fee Related
- 1999-06-09 EP EP99923974A patent/EP1002660B1/en not_active Expired - Lifetime
- 1999-06-09 US US09/423,335 patent/US6503604B1/en not_active Expired - Lifetime
- 1999-06-09 DE DE69932991T patent/DE69932991T2/de not_active Expired - Lifetime
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US6620470B2 (en) | 2000-08-31 | 2003-09-16 | Konica Corporation | Ink jet recording media |
EP1612054A1 (en) | 2004-07-02 | 2006-01-04 | Fuji Photo Film Co., Ltd. | Inkjet recording medium |
EP1655142A1 (en) | 2004-10-12 | 2006-05-10 | Mitsubishi Paper Mills Limited | Ink-jet recording material and method for preparing the same |
EP2106923A1 (en) | 2008-03-31 | 2009-10-07 | FUJIFILM Corporation | Inkjet recording medium and method of producing the same |
Also Published As
Publication number | Publication date |
---|---|
EP1002660B1 (en) | 2006-08-30 |
JP3694896B2 (ja) | 2005-09-14 |
DE69932991T2 (de) | 2007-03-08 |
US6503604B1 (en) | 2003-01-07 |
DE69932991D1 (de) | 2006-10-12 |
EP1002660A4 (en) | 2004-07-28 |
EP1002660A1 (en) | 2000-05-24 |
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