JP2002127586A - Method of recording ink jet image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of recording an ink jet image wherein an image forming layer of an ink recording material is excellent in a speed of absorption of water-based ink and is hardly cracked or flawed and wherein the image formed is hardly blurred with moisture and further ink is hardly transferred when the materials are laid on each other, in particular. SOLUTION: In this method of recording the ink jet image, the image is recorded on the ink recording material having on a substrate the image forming layer having voids, by using a water-based ink composition which contains an oil-soluble dye and has the polymer particulates dispersed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet image recording method, and more particularly, to a method of recording an image on an image forming layer of an ink recording material using an aqueous ink composition. The present invention relates to a difficult inkjet image recording method.

[0002]

2. Description of the Related Art Various methods have been developed for ink-jet image recording. These methods can be broadly divided into a method using an aqueous ink containing a water-soluble dye, a method using an ink containing an oil-soluble dye, and a method using an ink containing a dye. There is a method in which a wax ink containing a low melting point solid wax is melted by heat and used. Each of these methods is a method of forming and recording an image by discharging (ink-jetting) ink as liquid fine droplets on an ink recording medium.

[0003] In these ink jet image recording methods, it is desired that the ink is quickly absorbed and there is no bleeding of the ink in order to obtain a precise image, and various proposals have hitherto been made. For example, it has been studied to provide an image forming layer on a support of an ink recording material.
146786 discloses the use of an absorbent polymer for the image forming layer, JP-A-56-80489 discloses the use of a soluble or swellable substance, and a large number of polymers (polyvinyl alcohol (PVA), polyvinyl alcohol). It has been proposed to use pyrrolidone (PVP), polyethylene oxide (PEO), carboxymethyl cellulose (CMC) and the like. However, in each case, the effect of penetration of the aqueous ink by the hydrophilic group or the dissociable group of the polymer is used, and the ink absorption rate of the ink receiving layer is poor, and the robustness of the ink receiving layer under high humidity is low. It had disadvantages such as deterioration.

A method of absorbing ink by capillary action by forming the image forming layer as a porous film is disclosed in Japanese Patent Publication No. Sho 63-163.
No. 22997, No. 63-56876, Tokuhei 3-4
No. 8867, JP-A-57-14091, JP-A-60-61
Nos. 286 and 62-227684 and JP-A-7-27.
No. 6789. In each case, a large amount of hard inorganic fine particles are used to form voids, and an image forming layer is formed using a resin as a binder. Although these image forming layers are preferable in terms of ink absorbability, they are fragile and easily cracked or scratched, and there is no need for a recording medium having an image forming layer that can withstand severe use conditions without brittleness, cracking or scratching. ing.

[0005] On the other hand, inks applicable to the ink jet image recording method are used in conformity with the above-mentioned recording medium and image recording method, and include aqueous inks, pigment inks, low-melting solid wax inks containing dyes, oil-soluble dye inks and the like. Various things are known. Aqueous inks containing a water-soluble dye have the advantage that nozzle clogging is unlikely to occur, but formed images tend to bleed and have poor water resistance. An ink containing a pigment is less likely to bleed and has good water resistance, but the image quality is poor and nozzle clogging is likely to occur. A wax ink containing a low-melting-point solid wax containing a dye is complicated by attaching it to a recording member and then thermally melting it to complete an image. Inks containing oil-soluble dyes include oil-based inks that use an oil-based medium such as an organic solvent and water-based inks that use an aqueous medium. The development of a water-based ink which is excellent in water resistance with less bleeding is desired. In particular, an aqueous ink in which an oil-soluble dye is impregnated in polymer fine particles is expected to be resistant to bleeding, excellent in water resistance, and hard to cause nozzle clogging. Examples of such an aqueous ink include, for example, JP-A-54-5850.
No. 4 discloses an ink using polymer fine particles impregnated with an oil-soluble dye by adding an oil-soluble dye dissolved in an organic solvent to a latex obtained by emulsion polymerization of a vinyl monomer, stirring and evaporating the organic solvent. . Also, Japanese Patent Application Laid-Open No. 55-1
No. 39471, No. 62-172076, No. 62-18
No. 4072 and the like disclose an ink using polymer fine particles obtained by adding an oil-soluble dye to latex (polymer fine particles) obtained by emulsion-polymerizing a vinyl monomer with a low molecular surfactant and heating and stirring.

However, inks in which these oil-based inks are impregnated with fine polymer particles are not only resistant to bleeding, are excellent in water resistance, and are less likely to cause nozzle clogging.
When the members are superimposed and stored after being adhered and recorded on the recording member, a part of the adhered image may be transferred to the superimposed partner, so that an ink that is difficult to be transferred and an ink recording medium that is difficult to be transferred are required. Have been.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an image recording layer of an ink recording material which has an excellent water-based ink absorption rate, is hardly cracked or scratched, Another object of the present invention is to provide an ink jet image recording method in which a formed image is less likely to bleed due to moisture, and in particular, ink is difficult to transfer even when superimposed.

[0008]

The above object of the present invention is achieved by the following constitution.

1. An ink-jet image recording method, comprising: performing image recording on an ink recording material having a support and an image forming layer having voids, using an aqueous ink composition in which polymer fine particles containing an oil-soluble dye are dispersed.

[0010] 2. 2. The ink jet image recording method according to 1, wherein the water absorption capacity of the image forming layer is larger than the void capacity in a dry state.

3. The void volume of the image forming layer in the water absorbing state is
3. The ink-jet image recording method according to 1 or 2, wherein the void volume is larger than a void volume in a dry state.

4. The inkjet image recording method according to any one of claims 1 to 3, wherein the voids are formed using at least a swellable polymer and non-swellable polymer fine particles.

5. 5. The ink jet image recording method according to 4, wherein the swellable polymer has a crosslinked structure.

6. 4. The inkjet image recording method according to any one of claims 1 to 3, wherein the voids are formed using at least a water-soluble polymer, a crosslinking agent, and non-swellable polymer fine particles.

[0015] 7. The film thickness (D ₂₀ ) of the image forming layer at a relative humidity of 20% and the film thickness (D ₈₀ ) at a relative humidity of 80%
And the thickness change rate _{= ((D 80 -D 20)} / D 20) × 10
The inkjet image recording method according to any one of claims 1 to 6, wherein 0 (%) is 3% or more and 20% or less.

8. The polymer fine particles containing an oil-soluble dye contain 5 to 40% by mass of a monomer having an active methylene group.
Any one of 1 to 7, characterized in that the contained monomer composition is polymerized in the presence of a reactive emulsifier.
Item 10. The ink jet image recording method according to item 8.

9. The ink-jet image recording method according to any one of claims 1 to 8, wherein the polymer fine particles containing the oil-soluble dye are polymerized in an aqueous medium in the presence of the oil-soluble dye.

10. The inkjet image recording method according to any one of claims 1 to 9, wherein the support is a transparent support.

11. Wherein the image recording method is an inkjet image recording method for medical diagnosis.
0. The inkjet image recording method according to any one of 0.

Hereinafter, the present invention will be described in detail. First, the ink recording material of the present invention will be described.

The void volume of the image forming layer of the ink recording material of the present invention can be determined as follows.

Void volume = (apparent volume per unit area) − (actual volume per unit area) Here, actual volume per unit area = (mass of image forming layer per unit area) / (image forming layer) (Average value of specific gravity of materials constituting ink) The water absorption capacity of the image forming layer of the ink recording material of the present invention is 2
A sample whose mass was left standing at 3 ° C. and 20 RH% for 2 days (dry state) was immersed in ion-exchanged water at 23 ° C. for 10 seconds (water absorbing state), and the surface was lightly suppressed with filter paper to reduce the surface moisture. The wiping mass is measured, the increased mass is divided by the unit area to determine the mass of water absorption per unit area, and divided by the specific gravity of water to obtain the water absorption capacity. When the support is a water-absorbing material such as paper, the section where the support is directly exposed is sealed with a hydrophobic resin for measurement.

The dry state of the image forming layer of the ink recording material of the present invention (when left at 23 ° C. and 20 RH% for 2 days)
The pore volume in the water-absorbed state (when immersed in ion-exchanged water at 23 ° C. for 10 seconds) is larger than the void volume of the three-dimensional structure of the material forming the image forming layer having the voids in the dry state and the water-absorbent state. More specifically, the material that absorbs water swells in the water-absorbing state, and as a result, the distance between the materials that do not absorb water increases (differing between the dry state and the water-absorbing state). Such a change
It can be known by using a device such as Cryosem which freezes the sample in a water-absorbed state and observes it with an electron microscope.

The rate of change of the film thickness between the image forming layer of the ink recording material of the present invention at a relative humidity of 20% and the film thickness at a relative humidity of 80% can be measured as follows.

The film thickness (D ₂₀ ) at a relative humidity of 20% refers to the film thickness (unit: μm) of a support provided with humidity control at 23 ° C. and 20% RH for 2 days or more and an image forming layer provided on the support. ).

The film thickness (D ₈₀ ) at a relative humidity of 80% refers to the film thickness (unit: μm) of a support provided with humidity control at 23 ° C. and 80% RH for 2 days or more and an image forming layer provided on the support. ).

The rate of change of the film thickness is calculated by the following equation. Thickness change rate _{= ((D 80 -D 20)} / D 20) × 100
(%) The non-swellable polymer fine particles preferably used for forming voids in the image forming layer of the ink recording material of the present invention have a particle diameter of 0.1%.
It is not particularly limited as long as it is from 0.05 to several μm and does not swell with water, but is preferably a hydrophobic polymer fine particle, and preferably an aqueous dispersion of a hydrophobic polymer (hereinafter also referred to as a resin). As the aqueous dispersion of the resin, an aqueous dispersion of an acrylic resin, a polyester resin, rubbers, polyvinyl acetates, modified polyvinyl alcohol, cellulose esters, polyurethanes, polyvinyl chlorides, polyvinylidene chlorides, etc. Can be mentioned.

Among these resins, a resin having an active methylene group and a resin having a cationic group can be preferably used.

Examples of the polymer having an active methylene group include a repeating unit derived from an ethylenically unsaturated monomer having an active methylene group, methacrylic acid ester,
A polymer having a repeating unit derived from an ethylenically unsaturated monomer selected from an acrylate ester, a maleate ester, and a diene can be mentioned, and a polymer represented by the following general formula is preferable.

In the general formula [1]-(A) _x- (B) _y- (C) _z- , A represents an ethylenically unsaturated monomer having an active methylene group represented by the following general formula [2]. B represents a repeating unit to be derived, and B is a homopolymer having a glass transition temperature of 3
Represents a repeating unit derived from an ethylenically unsaturated monomer selected from methacrylic acid esters, acrylic acid esters, maleic acid esters and dienes having a temperature of 5 ° C. or lower, and C is derived from an ethylenically unsaturated monomer other than A and B. Represents a repeating unit. Here, x, y, and z represent the mass percentage ratio of each component in the polymer, and each is 0.5%.
≦ x ≦ 41, 0 ≦ y ≦ 59, x + y + z = 100.

[0031]

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In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X represents a monovalent group containing an active methylene group.

In the polymer represented by the general formula [1], an ethylenically unsaturated monomer having an active methylene group represented by A is exemplified, but is not limited thereto.

MN-1 2-acetoacetoxyethyl methacrylate MN-2 2-acetoacetoxyethyl acrylate MN-3 2-acetoacetoxypropyl methacrylate MN-4 2-acetoacetoxypropyl acrylate MN-5 2-acetoacetamidoethyl methacrylate MN- 6 2-acetoacetamidoethyl acrylate MN-7 2-cyanoacetoxyethyl methacrylate MN-8 2-cyanoacetoxyethyl acrylate MN-9 N- (2-cyanoacetoxyethyl) acrylamide MN-10 2-propionylacetoxyethyl acrylate MN-11 N- (2-propionylacetoxyethyl) methacrylamide MN-12 N-4- (acetoacetoxybenzyl) phenylacrylamide MN-13 Ethyl acryloyl acetate MN-14 Acryloyl methyl acetate MN-15 N-methacryloyloxymethyl acetoacetamide MN-16 Ethyl methacryloyl acetoacetate MN-17 N-allyl cyanoacetamide MN-18 Methyl acryloylacetoacetate MN-19 N- (2-methacryloyl) Oxymethyl)
Cyanoacetamide MN-20 p- (2-acetoacetyl) ethylstyrene MN-21 4-acetoacetyl-1-methacryloylpiperazine MN-22 ethyl-α-acetoacetoxymethacrylate MN-23 N-butyl-N-acryloyloxyethyl acetoate Acetamide MN-24 p- (2-acetoacetoxy) ethylstyrene An ethylenically unsaturated monomer giving a repeating unit represented by B in the general formula [1] has a homopolymer having a glass transition temperature of 35 ° C. or lower. Such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, iso-nonyl acrylate, dodecyl acryle Alkyl methacrylate (eg, n-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, iso)
-Nonyl methacrylate, dodecyl methacrylate, etc.), dienes (for example, butadiene, isoprene), and maleic acid ester.

When the polymer (fine particles) represented by the general formula [1] is emulsion-polymerized, a water-soluble polymer as an emulsifier may be used. As the water-soluble polymer, a natural polymer or a semi-synthetic water-soluble polymer may be used. Including, for example, alginic acid or a salt thereof, dextran, dextran sulfate, glycogen, gum arabic, albumin, agar, a starch derivative, carboxymethylcellulose or a salt thereof, hydroxycellulose,
Cellulose sulfate and the like can be mentioned, but derivatives thereof can also be used.

The following are examples of such water-soluble polymers.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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In the emulsion polymerization, depending on the purpose,
Wide range of polymerization initiator, concentration, polymerization temperature, reaction time, etc.
Needless to say, it can be easily changed. Also,
The emulsion polymerization reaction may be carried out by putting the monomer, the surfactant, the water-soluble polymer, and the medium in advance in a container, and adding the initiator, or dropping a part or the whole amount of each component as necessary. The polymerization may be carried out while performing the polymerization.

In the polymer represented by the general formula [1], US Pat. No. 3,459,790 and US Pat. No. 619, 195,
3,929,482 and 3,700,456, West German Patent 2,442,165, European Patent 13,147
No., JP-A-50-73625 and JP-A-50-146331.
References such as numbers can also be made.

The polymer latex having an active methylene group, which is preferable as the non-swellable polymer fine particles preferably used for forming voids in the image forming layer of the ink recording material of the present invention, is exemplified below by the composition ratio of each component in the copolymer. However, the present invention is not limited to these.

[0046]

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Here, S-2 is sodium dodecylbenzenesulfonate, BA is butyl acrylate, St is styrene, EA is ethyl acrylate, EMA is ethyl methacrylate, VAc is vinyl acetate, and AIN is iso-
Nonyl acrylate, CHMA represents cyclohexyl methacrylate.

The polymer having a cationic group, which is preferable as the non-swellable polymer fine particles preferably used for forming voids in the image forming layer of the ink recording material of the invention, includes
A resin having a quaternary amine group is preferable, and a resin represented by the following general formula [3] or [4] is preferably used.

[0049]

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In the formula, A1 represents a polymerizable monomer unit having at least two ethylenically unsaturated groups;
1 represents a copolymerizable monomer unit having an ethylenically unsaturated group. Q represents N or P, R ₁ , R ₂ , R ₃
Each represents an alkyl group, M ^- is an anion.
Here, x1, y1, z1 represent the mole percentage ratio of each component in the polymer, and x1 is 0.25 to 5 mol%, y
1 represents 0 to 90 mol%, z1 represents 10 to 99 mol%,
x1 + y1 + z1 = 100 mol%.

Examples of A1 include ethylene glycol diacrylate, ethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,
Pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate,
Glycerol acroxydimethacrylate, 1,1,1
-Trishydroxymethylethane diacrylate, 1,
1,1-trishydroxymethylethanetrimethacrylate, 1,1,1-trishydroxymethylethanedimethacrylate, 1,1,1-trishydroxymethylethanetrimethacrylate, 1,1,1-trishydroxymethylethanetrimethacrylate, 1,1,1-trishydroxymethylpropane diacrylate, 1,1,1
-Trishydroxymethylpropane diacrylate,
Examples thereof include 1,1,1-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, and divinylbenzene.

Examples of B1 include acrylates (for example, methyl acrylate, ethyl acrylate,
Butyl acrylate, hexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, is
o-nonyl acrylate, dodecyl acrylate, t-
Butyl acrylate, phenyl acrylate, 2-naphthyl acrylate, etc.), methacrylates (for example, butyl methacrylate, hexyl methacrylate,
2-ethylhexyl methacrylate, iso-nonyl methacrylate, dodecyl methacrylate methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate, ethylene Glycol dimethacrylate, etc.), vinyl esters (eg, vinyl benzoate, pivaloyloxyethylene, etc.), acrylamides (eg, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide) ,
Benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, diacetoneacrylamide, etc.), methacrylamides (for example, methacrylamide, methylmethacrylamide, ethyl) Methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide,
Phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, etc.), styrenes (for example, styrene,
Methyl styrene, dimethyl styrene, trimethylene styrene, ethyl styrene, isopropyl styrene, chloro styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate), divinyl benzene, acrylonitrile, meta Acrylonitrile, N-vinylpyrrolidone, N-vinyloxazolidone, vinylidene chloride, phenyl vinyl ketone and the like can be mentioned. These monomers may be used alone or in combination of two or more.

The polymer latex having a cationic group, which is preferable as the non-swellable polymer fine particles preferably used for forming the voids in the image forming layer of the ink recording material of the present invention, is exemplified below, but is not limited thereto. Absent.

[0054]

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These polymer fine particles can be similarly synthesized by the above-mentioned method, and can be obtained by dispersing a resin in water, self-emulsifying in water, or a suspension polymerization method, in addition to the latex polymerization. These resin dispersions may be used alone or in combination of a plurality of types.

The swellable polymer preferably used for forming voids in the image forming layer of the ink recording material of the present invention includes:
An organic polymer or an inorganic polymer can be given.

As the organic polymer, crosslinked gelatin is preferably used, but other crosslinked hydrophilic polymers can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate, sodium alginate, cellulose sulfate, dextrin, dextran, dextran Sugar derivatives such as sulfates, poly-N-
A crosslinked product of a single kind of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, or a variety of synthetic hydrophilic polymers such as copolymers can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used in combination, and a hydrolyzate of gelatin and an enzyme-decomposed product of gelatin can also be used.
These hydrophilic polymers may be used alone or in a plurality of types. The swellability is not particularly limited as long as the apparent volume is increased by absorbing water, but the apparent volume increase rate is preferably 1.2 times or more, more preferably 1.4 times or more.

The crosslinking may be carried out by using a crosslinking agent or by self-crosslinking of a polymer. The crosslinking agent used in the organic polymer is not particularly limited as long as it can impart swelling properties.For example, aldehydes such as formaldehyde, glyoxal, glutaraldehyde, succinaldehyde, mucochloric acid, mucohalic acids such as mucobromic acid, dimethylol urea N-methylols, dichloro-s-
Examples include triazines, active ethylenes having a vinyl sulfone group, an acrylamide group, and the like, ethylene imines, epoxies, and carbodiimides. In order to obtain crosslinked gelatin, dichloro-s-triazines, vinylsulfone-type active ethylenes, and carbodiimides are preferably used.

Examples of the inorganic polymer include crosslinked water glass. Water glass is SiO ₂ / N
a ₂ O and / or SiO ₂ / K ₂ O,
Water glass whose molar ratio of O ₂ / Na ₂ O and / or SiO ₂ / K ₂ O is preferably in the range of 1 to 5. The crosslinking agent (curing agent) used in these is not particularly limited as long as it is a known alkali water glass curing agent or a water-soluble chemical substance having a reaction function thereof.
Inorganic salts represented by hydrochloric acid, nitric acid, sulfuric acid, boric acid, phosphoric acid, etc., water-soluble bisulfates, water-soluble bicarbonates, water-soluble acid sulfates, water-soluble acid phosphates, etc., Water-soluble organic acids and water-soluble organic curing agents that release acids that can be slowly released in alkalis can be used.

The mass ratio of the non-swellable polymer fine particles to the swellable polymer is usually at least 1/1, but is preferably
4/1 to 20/1.

The support of the present invention is not particularly restricted but includes, for example, plastic films such as polyethylene terephthalate, polyethylene naphthalate and triacetyl cellulose, papers such as polyethylene coated paper and coated paper, glass and the like. it can. When the image recording method of the present invention is used for an ink jet image recording material for medical diagnosis, these supports must have transparency. If necessary, a blue dye commonly used for medical images may be contained. These supports may be provided with a subbing layer on the surface for adhesion of the image forming layer, or may be subjected to corona discharge, glow discharge, ultraviolet irradiation or the like. When the hydrophilic binder is gelatin, known undercoating can be used for silver halide photographic materials.

The image forming layer of the present invention can be formed by any method, and can be obtained by coating a coating solution of an aqueous medium and then drying it. As a coating method,
A bread coater coating method, a reverse roller coating method, an air doctor coating method, a knife coater coating method, a squeeze coater coating method, a bar coater coating method, a curtain coating method, an extrusion coating method, a slide hopper coating method, and the like can be used. The drying conditions are not particularly limited, but preferably the temperature of the coating surface is not higher than the glass transition temperature of the resin + 20 ° C. Alternatively, the coating film surface may be cooled and then dried immediately after the application. The thickness of the layer after drying is preferably 5 to 100 μm, and may be formed by a single layer or a multilayer coating. In the case of a multi-layer, it may be formed by applying a coating solution composed of exactly the same composition in multiple layers, or may be formed by layering coating solutions having different compositions. In the formation of a multi-layer, a sequential coating in which a single layer is applied and dried followed by a further drying may be used, or a simultaneous application may be performed.

A matting agent can be used in the image forming layer of the present invention. The particle size of the matting agent is not particularly limited as long as the matting agent comes out of the coating film surface and can form irregularities on the surface. Further, the matting agent is distinguished from non-swellable polymer fine particles preferably used in the present invention by forming irregularities on the surface after coming out of the coating film surface. In addition, a surfactant, a fluorine-based surfactant, and a sliding agent such as silicone and wax commonly known in silver halide photographic materials can be used.

Next, the aqueous ink composition of the present invention will be described. The aqueous medium in the aqueous ink composition of the present invention,
The liquid is mainly composed of water, but may contain a water-soluble organic solvent if necessary. Examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-
Propanol, 1-pentanol, 2-pentanol,
3-pentanol, 2-methyl-1-butanol, 3-
Monohydric alcohol compounds such as methyl-1-butanol, 2-methyl-2-butanol and 3-methyl-2-butanol, ethylene glycol, polyethylene glycol,
Propylene glycol, triethylene glycol, polytriethylene glycol, tetraethylene glycol,
Examples include polyhydric alcohol compounds such as polytetraethylene glycol, 1,3-butanediol, glycerin, and 1,2,6-hexanetriol. One of these water-soluble organic solvents may be used, or two or more water-soluble organic solvents may be used in combination. The addition amount of these water-soluble organic solvents is preferably 0.1 to 20.0% by mass of the aqueous ink composition.

The polymer fine particles of the aqueous ink composition of the present invention are preferably polymer particles having a particle size of 0.05 to several μm, and include fine particles in which a resin is dispersed in an aqueous medium. Examples of the resin include acrylic resins, polyester resins, rubbers, polyvinyl acetates, modified polyvinyl alcohols, cellulose esters, polyurethanes, polyvinyl chlorides, polyvinylidene chlorides, and the like. As a method for dispersing the resin in the aqueous medium, there are a method in which the resin is polymerized in advance and the resin is dispersed in the aqueous medium, and a method in which the monomer is prepared by an emulsion polymerization method and a suspension polymerization method in the aqueous medium. And a suspension polymerization method. The components of the aqueous medium used when forming the polymer fine particles may be the same as or different from the components used when finally preparing the ink.

The polymer having an active methylene group which is preferably used as the polymer fine particles of the aqueous ink composition of the present invention includes a repeating unit derived from an ethylenically unsaturated monomer having an active methylene group, a methacrylic acid ester and an acrylic acid ester. And a polymer having a repeating unit derived from an ethylenically unsaturated monomer selected from maleic acid esters and dienes, and is preferably the same as the polymer represented by the general formula [1].

The polymer having active methylene groups (polymer fine particles) preferably used as the polymer fine particles of the aqueous ink composition of the present invention preferably contains 5 to 40% by mass of the monomer composition having active methylene groups, More preferably, the content is 30% by mass. 5
When the content is less than 10% by mass, the content of the active methylene group is small, and when the ink composition is ejected, the water resistance of the ink composition in the image forming layer may be insufficient. The Tg (glass transition temperature) of the polymer fine particles is lowered, and when the ink composition is ejected, problems such as stickiness of the image forming layer and poor drying may occur, and the finish may be poor.

The reactive emulsifier preferably used in the polymerization production of the polymer fine particles of the aqueous ink composition of the present invention is not particularly limited, either anionic or nonionic reactive emulsifiers. Allyl group,
Reactive emulsifiers having a radically polymerizable unsaturated group such as a (meth) acryl group and a styryl group may be mentioned, and may be used alone or in combination of two or more kinds when polymerizing and producing polymer fine particles.

The anionic reactive emulsifier includes, for example, reactive emulsifiers represented by the following general formulas [5] to [8].

[0070]

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[0071] In the formula, R ² represents hydrogen or a methyl group, R ³
Represents an alkyl group, alkenyl group, aryl group or aralkyl group having 6 to 18 carbon atoms, R ⁴ represents hydrogen or a methyl group, and R ⁵ represents an alkyl group, alkenyl group, aryl group or aralkyl group having 6 to 18 carbon atoms. X represents a single bond or a methylene group; M represents an alkali metal;
Is an integer of 1 to 50, n is an integer of 1 to 50, q is 0 or 1.
Represents

Specific examples of the anionic reactive emulsifier represented by the general formula [5] include, for example, “Adecaria Soap SE-10N” and “Adecaria Soap SE-2”.
0N "," Adecaria Soap SE-30N "
Asahi Denka Kogyo Co., Ltd.]; specific examples of the anionic reactive emulsifier represented by the general formula [6] include:
Aqualon HS-05, Aqualon HS-1
0 "," AQUARON HS-20 "," AQUARON H "
S-30 "(above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); specific examples of the anionic reactive emulsifier of the above general formula [7] include, for example," Latemul S-120 "," Latemul S "
-120A "," Latemul S-180 "," Latemul S-180A "(all manufactured by Kao Corporation)," Eleminol JS-21 "(manufactured by Sanyo Chemical Industry Co., Ltd.), etc .; And the like. Specific examples of the anionic reactive emulsifier of the present invention include, for example, "ANTOX MS-60" (manufactured by Nippon Emulsifier Co., Ltd.).

Other anionic reactive emulsifiers include, for example, alkyl alkenyl succinate ester-based reactive emulsifiers such as "Latemul ASK" (manufactured by Kao Corporation); for example, "Eleminol RS-30" [Sanyo Chemical Industries, Ltd.] Polyoxyalkylene (meth) acrylate sulfate ester-based reactive emulsifier;
Polyoxyalkylene alkyl ether aliphatic unsaturated dicarboxylic acid ester-based reactive emulsifiers such as "1120", "RA-2614" (all manufactured by Nippon Emulsifier Co., Ltd.);
For example, a (meth) acrylic acid sulfoalkyl ester salt type reactive emulsifier such as "Antox MS-2N" (manufactured by Nippon Emulsifier Co., Ltd.); a dihydroxyalkyl phthalate (meth) acrylate sulfate ester type reactive emulsifier;
For example, "H-3330PL" (Daiichi Kogyo Seiyaku Co., Ltd.)
And mono- or di- (glycerol-1-alkylphenyl-3-allyl-2-polyoxyalkylene ether) phosphate ester-based reactive emulsifiers.

Examples of the nonionic reactive emulsifier include reactive emulsifiers represented by the following general formulas [9] and [10].

[0075]

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[0076] In the formula, R ² represents hydrogen or a methyl group, R ³
Represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group having 6 to 18 carbon atoms; R ⁴ represents hydrogen or a methyl group; X represents a single bond or a methylene group;
Represents an integer of 50.

Specific examples of the nonionic reactive emulsifier represented by the general formula [9] include, for example, “Adecaria soap NE-10” and “Adecaria soap NE-2”.
0, Adecaria Soap NE-30 "(manufactured by Asahi Denka Kogyo Co., Ltd.) and the like; specific examples of the nonionic reactive emulsifier represented by the general formula [10] include" Aqualon RN " -10 "," AQUARON RN-2 "
0 "," AQUARON RN-30 "," AQUARON R
N-50 "(both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); and the like.

Examples of other nonionic reactive emulsifiers include “RMA-564” and “RMA-568”.
Polyoxyalkylene alkyl phenyl ether (meth) acrylate-based reactive emulsifiers such as [manufactured by Nippon Emulsifier Co., Ltd.]; polyoxyalkylene alkyl phenyl ethers such as "RMA-1114" [manufactured by Nippon Emulsifier Co., Ltd.] (Meth) acrylate-based reactive emulsifiers;

Among these reactive emulsifiers, an anionic reactive emulsifier is used because it is easy to obtain a small particle size suitable as polymer fine particles (aqueous dispersion) of the aqueous ink composition of the present invention. It is desirable that it has excellent copolymerizability with the monomer used in the present invention, has little unreacted residue even when used in large amounts, and has properties such as corrosion resistance of the resulting aqueous coating composition coating film. Glycerol-1-allyl-3-alkylphenyl-2-polyoxyethylene sulfate ester-based anionic reactive emulsifier represented by the above general formula [5] because of little inhibition of It is particularly preferable to use a polyoxyethylene alkyl alkenyl phenyl ether sulfate ester type anionic reactive emulsifier represented by the formula [6].

The amount of the reactive emulsifier to be used is generally 0.1 to 100 parts by mass of the total amount of the monomers used in the present invention.
1 to 30 parts by mass, preferably 2 to 25 parts by mass,
Particularly preferably, 3 to 20 parts by mass is used.

In the emulsion polymerization of the polymer fine particles of the aqueous ink composition of the present invention, the emulsion may be used together with the above-described reactive emulsifier, if necessary, in a range that does not adversely affect the performance of the resulting copolymer aqueous dispersion. Anionic and / or nonionic emulsifiers can be used in combination.

Examples of the above-mentioned ordinary nonionic emulsifiers include polyoxyethylene octyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; and polyoxyethylene alkyl phenyl such as polyoxyethylene nonyl phenyl ether. Ethers; for example, higher sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, and sorbitan trioleate; higher polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate;
For example, polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; for example, polyoxyethylene-polyoxypropylene -Block copolymers; and the like.

Examples of the above-mentioned usual anionic emulsifiers include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate esters such as sodium lauryl sulfate; For example, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkyl aryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate; sodium monooctyl sulfosuccinate, dioctyl Alkyl sulfosuccinate salts such as sodium sulfosuccinate and sodium polyoxyethylene lauryl sulfosuccinate, and derivatives thereof; and the like. Door can be.

When these ordinary emulsifiers are used in combination with the reactive emulsifiers, these ordinary emulsifiers may be used in combination as appropriate, and the amount used is from 0 to 1 part by mass per 100 parts by mass of the monomer. Preferably it is.

In the emulsion polymerization of the polymer fine particles of the aqueous ink composition of the present invention, the above-described reactive emulsifier and any of the above-mentioned reactive emulsifiers used as necessary are used as long as they do not adversely affect the performance of the resulting copolymer aqueous dispersion. A water-soluble protective colloid can be used in combination with a usual anionic and / or nonionic emulsifier.

Examples of the above-mentioned water-soluble protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; and celluloses such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose salts and the like. And natural polysaccharides such as guar gum; and these can be used alone or in combination of two or more. The amount of the water-soluble protective colloid used is preferably from 0 to 10 parts by mass per 100 parts by mass of the total of the monomers.

In the emulsion polymerization, usually, for example,
Persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; t-butyl hydroperoxide;
Polymerization initiators such as organic peroxides such as cumene hydroperoxide and p-menthane hydroperoxide; hydrogen peroxide; These polymerization initiators can be used either in one kind or in a combination of two or more kinds. These polymerization initiators, based on a total of 100 parts by mass of the monomer,
It is preferable to use 0.1 to 1 part by mass.

In the emulsion polymerization, a reducing agent can be used together with the polymerization initiator, if desired. Examples of such a reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate metal salt; sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, and the like. Reducing inorganic compounds; and the like. It is preferable to use these reducing agents in an amount of 0.1 to 1 part by mass based on 100 parts by mass of the total of the monomers.

Further, a chain transfer agent can be used in the emulsion polymerization. Examples of such a chain transfer agent include dodecyl mercaptan, t-dodecyl mercaptan, butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, and trichlorobromomethane. These chain transfer agents are used in an amount of 0 to 100 parts by mass of the total amount of the monomers.
It is preferable to use 1 to 1 part by mass.

In the emulsion copolymerization, the copolymerization temperature suitably employed is preferably 40 to 100 ° C., and 60 to 9 ° C.
0 ° C. is particularly preferred.

The particle size of the polymer fine particles thus dispersed in the aqueous medium of the polymer aqueous dispersion has a particle size of 0.05
μm to several μm, preferably 0.06 to 1 μm
Is more preferable, and particularly preferably 0.1 to 0.2.

The oil-soluble dye of the present invention is not particularly limited as long as it is an oil-soluble dye. For example, monoazo oil-soluble dyes, anthraquinone oil-soluble dyes, disazo oil-soluble dyes, phthalocyanine oil-soluble dyes, metal Complex salt type monoazo oil-soluble dyes and triallylmethane oil-soluble dyes can be exemplified. One of these dyes may be used, or two or more oil-soluble dyes may be used in combination. The addition amount of these oil-soluble dyes is preferably 0.1 to 20% by mass of the ink composition. If necessary, a water-soluble dye may be used in combination.

Other additives can be added to the aqueous ink composition of the present invention according to each purpose. For example, a thickener, a fluidity improver, a surfactant, a conductivity adjuster, a pH adjuster, an antioxidant, an ultraviolet absorber, a preservative, a bactericide, a defoamer, a penetrant and the like can be mentioned. .

[0094]

EXAMPLES The present invention will be described below in detail with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 (Preparation of Ink Recording Material for Inkjet)
On the other hand, the following subbing first and second layers are sequentially provided on one side (A side) of a blue-colored polyethylene terephthalate film base (thickness: 175 μm), and the other side (B
Surface), a heat treatment was performed at 140 ° C. for 2 minutes.

Side A First layer Polymer latex 1 40 mg / m ² (solid content) Polymer latex 2 760 mg / m ² (solid content) Water-soluble polymer 1 40 mg / m ² Surfactant 16 mg / m ² Second layer Polymer Latex 3 300 mg / m ² (solid content) Water-soluble polymer 1 15 mg / m ² SP-15 600 mg / m ² Crosslinker 1 100 mg / m ² Surfactant 27 mg / m ² Silica fine particles 1 mg / m ² Polymer latex 1: Styrene-glycidyl methacrylate-n-butyl acrylate (20/40/40% by mass) copolymer latex Polymer latex 2: styrene-glycidyl methacrylate-n-butyl acrylate-acetoacetoxyethyl methacrylate (35/40/5/20% by mass) Polymerized polymer latex Polymer latte Box 3: Styrene-glycidyl methacrylate-n-butyl acrylate (40/40/20% by mass) copolymer latex Water-soluble polymer 1: sodium isoprenesulfonate-styrene copolymer

[0097]

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Side B Polymer Latex 4 500 mg / m ² Water-soluble polymer 1 25 mg / m ² Hydrophilic polyester 2000 mg / m ² Fine particles of polymethyl methacrylate (average particle size 10 μm) 120 mg / m ² Surfactant 35 mg / m ² Polymer Latex 4: Styrene-glycidyl methacrylate-n-butyl acrylate-acetoacetoxyethyl methacrylate (40/30/10/20 mass%) copolymer latex Hydrophilic polyester: dimethyl terephthalate, dimethyl isophthalate, 5 as dicarboxylic acid component -Polyester obtained by polycondensation of sodium sulfoisophthalsan dimethyl, 1,4-cyclohexyldicarboxylic acid and ethylene glycol as a diol component

[0099]

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Next, the image forming layer coating solution was applied to the surface A with a slide hopper, set and dried to provide the following image forming layer.

(First layer, Second layer) Non-swellable polymer fine particles (described in Table 1) (Amount described in Table 1) Swellable polymer or water-soluble polymer (described in Table 1) (Table 1) (Amount described in Table 1) Crosslinking agent (described in Table 1) (amount described in Table 1) (third layer) Non-swellable polymer fine particles (described in Table 1) (amount described in Table 1) Swellable polymer Or water-soluble polymer (described in Table 1) (amount described in Table 1) Crosslinking agent (described in Table 1) (amount described in Table 1) Polymethyl methacrylate fine particles having an average particle size of 15 μm 200 mg / m ² Surface activity Agent 3 8 mg / m ² Surfactant 4 8 mg / m ²

[0102]

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As described above, the ink recording materials 1 to 13
Was prepared. (Preparation of Ink Composition for Inkjet) Preparation of aqueous ink composition I-1 (the present invention) 5 g of MN-1 (2-acetoacetoxyethyl methacrylate), 15 g of ethylhexyl acrylate, 20 g of styrene, 0.8 g of acrylic acid, ethylene glycol Aizen Spil in a mixture of 1.0 g of methacrylate
On BlackMH special (8.0 g of oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd.) and 1.0 g of azobisdimethylvaleronitrile were dissolved, and this was dissolved in 18 g of ion-exchanged water as a reactive activator Eleminor JS-2.
5.3 g (manufactured by Sanyo Chemical Industry Co., Ltd.) was added to the dissolved aqueous solution, and the mixture was dispersed by ultrasonic waves. Temperature controller, heating device,
20 g of ion-exchanged water was placed in a container having a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and the inside of the container was replaced with nitrogen gas.
C., and the dispersion was added thereto over 3 hours with stirring. After completion of the addition, the mixture was stirred while maintaining the same temperature for 2 hours, then cooled, 322 g of water was added, and the aqueous ink composition (I -1) was prepared.

Preparation of aqueous ink composition I-2 (comparative) 20 g of ethyl acrylate, 20 g of styrene, 0.8 g of acrylic acid, 1.0 g of ethylene glycol methacrylate
Aizen Spiron Black M
8.0 g of H special (oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd.) and 1.0 g of azobisdimethyl valeronitrile are dissolved, and this is dissolved in 18 g of ion-exchanged water as a reactive activator Eleminor JS-2 (Sanyo Chemical Co., Ltd.). 5.3 g) was added to an aqueous solution in which 5.3 g was dissolved, and dispersed by ultrasonic waves. Place ion-exchanged water in a container having a temperature controller, a heating device, a stirrer, a reflux cooler,
Then, the inside of the vessel was charged with nitrogen gas and replaced with nitrogen gas and heated to 80 ° C., and the dispersion was added thereto over 3 hours with stirring, and after the addition was completed, the mixture was stirred at the same temperature for 2 hours, and then cooled, 322 g of water was added to obtain an aqueous ink composition (I-2).

Preparation of Aqueous Ink Composition I-3 (Comparative) 140 g of ion-exchanged water was added to a container having a temperature controller, a heating device, a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and the inside of the container was replaced with nitrogen gas. Then, the mixture was heated and stirred at 75 ° C. Add sodium dodecylbenzenesulfonate aqueous solution (solid content 2
0.3 g of a sulfonated isoprene-styrene copolymer and 5.5 g of an aqueous solution of a sulfonated product of a sulfonated isoprene-styrene copolymer (solid content: 36% by mass).
Then, a mixture of 5 g of 2-acetoacetoxyethyl methacrylate, 20 g of ethylhexyl acrylate, 15 g of styrene, 0.8 g of acrylic acid, and 1.0 g of ethylene glycol methacrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining the same temperature, and then cooled to obtain a polymer fine particle dispersion having an active methylene group. A
isen Spiron Black MH spec
ial (oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd.) 8.0
g was dissolved in 24 g of tricresyl phosphate, and this was added to the above-mentioned polymer fine particle dispersion while stirring, and further mixed with a high-speed mixer. 200 g of water was added to the obtained dispersion to obtain an aqueous ink composition (I-3). Evaluation method The following evaluation was performed on the prepared samples.

(Scratch strength) The tip diameter is 100 μm
Using a sapphire needle, the surface of the ink recording material sample was scratched while changing the weight, and the weight when the needle destroyed the image forming layer was measured.

(Crack) The prepared ink recording material was
After bending at 80 degrees and returning to the original flat state again, the state of cracks on the image forming layer surface was observed. A: No crack was found in the bent part. B: Slight crack was formed in the bent part. C: Bending All of the cracked portions were cracked. D: The bent portion was cracked and the image forming layer was peeled off.

(Ink Absorption Rate) The aqueous ink composition prepared on the surface of the image forming layer of the prepared ink recording material was printed 4 cm square all over by an ink jet printer (MJ-910C manufactured by Epson Corporation), and immediately after printing (about 10 Second), the paper is contacted, and the absorption speed of the ink to the medium (image forming layer) and the transfer state are checked. A: The ink absorption speed is fast, and the ink is not transferred. B: The ink absorption is fast. The ink was slightly transferred. C: The ink absorption was slow, and the ink was transferred. D: The ink flowed.

(Bleeding of Image) The aqueous ink composition prepared was printed 4 cm square on the image forming layer surface of the prepared ink recording material by an ink jet printer (described above). Printed sample at 23 ° C, relative humidity 80%
After storage for 72 hours in the environment of No. 1, the number of protrusions due to ink bleeding from the printed portion was observed with a Shakasten. A: None B: Less than 5 C: 5 to 20 D: More than 20 .

(Transfer of Ink by Overlay) The aqueous ink composition prepared on the image forming layer surface of the prepared ink recording material by ink jet printer (described above)
Solid printing was performed on 0 cm square. After conditioning the printed sample for 4 hours in an environment of 23 ° C. and a relative humidity of 80%,
PPC paper, which was similarly humidified, was placed on the printing surface, and
A weight was placed so as to give a pressure of 45 × 10 ³ Pa, and the degree of ink transfer to paper after 24 hours was observed. A: No transfer B: Some transfer was observed (transferred in dots) C: Transfer was confirmed It was evaluated as possible (more than half of the printed portion was transferred).

The above processes and results are shown in Tables 1 and 2.

[0112]

[Table 1]

GEL: Gelatin PVA: Polyvinyl alcohol (PVA 217, manufactured by Kuraray Co., Ltd.) (Note 1): Using the polymer latex 4

[0114]

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[0115]

[Table 2]

As is clear from Tables 1 and 2, by using the ink recording material (image forming layer) and the ink composition of the present invention, the image forming layer has high scratch strength (scratch resistance) and cracks. It can be seen that the ink transfer characteristics are small, the ink absorption characteristics are excellent, the image bleeding is small, and the transfer of the ink due to the superposition is particularly suppressed.

[0117]

According to the present invention, the image forming layer of the ink recording material has an excellent aqueous ink absorption rate, is hardly cracked or scratched, and the formed image is less likely to bleed due to moisture. It is possible to provide an inkjet image recording method that is difficult to perform.

Claims (11)

[Claims] 1. An image recording method, comprising using an aqueous ink composition in which polymer fine particles containing an oil-soluble dye are dispersed in an ink recording material provided with an image forming layer having voids on a support. Ink jet image recording method. 2. The ink jet image recording method according to claim 1, wherein the water absorption capacity of the image forming layer is larger than the void capacity in a dry state. 3. The ink-jet image recording method according to claim 1, wherein the water-absorbing void volume of the image forming layer is larger than the dry void volume. 4. The ink-jet image recording according to claim 1, wherein the void is formed by using at least a swellable polymer and non-swellable polymer fine particles. Method. 5. The ink jet image recording method according to claim 4, wherein the swellable polymer has a crosslinked structure. 6. The method according to claim 1, wherein the void is formed by using at least a water-soluble polymer, a crosslinking agent, and non-swellable polymer fine particles. Ink jet image recording method. 7. The rate of change of the film thickness of the image forming layer between the film thickness (D ₂₀ ) at a relative humidity of 20% and the film thickness (D ₈₀ ) at a relative humidity of 80% = ((D ₈₀ −D ₂₀ )) / D ₂₀₎ × 100
The inkjet image recording method according to any one of claims 1 to 6, wherein (%) is 3% or more and 20% or less. 8. The polymer fine particles containing an oil-soluble dye may contain 5 to 40% by mass of a monomer having an active methylene group.
The inkjet image recording method according to any one of claims 1 to 7, wherein the contained monomer composition is polymerized in the presence of a reactive emulsifier. 9. The ink jet according to claim 1, wherein the polymer fine particles containing the oil-soluble dye are polymerized in an aqueous medium in the presence of the oil-soluble dye. Image recording method. 10. The inkjet image recording method according to claim 1, wherein the support is a transparent support. 11. The method according to claim 1, wherein the image recording method is an inkjet image recording method for medical diagnosis.
11. The inkjet image recording method according to any one of items 10 to 10.