JP2003266924A - Composition for ink jet recording medium and recording medium using composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an ink jet recording medium which shows a significant economy and a high liquid stability and forms an image recording layer with ink absorption characteristics, luster, dryness and water resistance and further, produces an ultra-sharp image, as a useful material for ink jet recording, when the composition is used as an ink receiving layer, and a recording medium using this composition. <P>SOLUTION: This composition constitutes an image receiving layer formed on at least one side of a base material. In addition, the composition comprises a cationic acrylic copolymer (A) containing 1 to 50 pts.mass of a crosslinking group and a cationic resin-modified silica dispersion(B) containing 50 to 90 pts.mass of silica with an average flocculation particle diameter of less than 200 nm. In addition, the recording medium using said composition and the like are provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inkjet recording composition using a crosslinkable cationic acrylic copolymer and a cationic resin-modified silica dispersion, and a substrate using the recording composition. The present invention relates to a recording body on which an image receiving layer is formed.

[0002]

2. Description of the Related Art Inkjet recording systems are inexpensive and
Since it is easy to make full color, has low noise, and is excellent in printing quality, it is rapidly spreading in recent years. A water-based ink is mainly used for inkjet recording from the viewpoint of safety and recording suitability, and recording is performed by ejecting ink dots from a nozzle toward a recording sheet. Therefore, the recording sheet is required to absorb the ink promptly. Further, by making the ink multi-colored and making the ink dots smaller in particle size, it has become possible to obtain a recording comparable to that of a silver salt photographic image, and the recording speed has also been increased. As described above, although the recording apparatus and the recording method have been improved, correspondingly, the inkjet recording material is required to have a high level of characteristics.

Various recording papers have been conventionally used as ink jet recording materials. For example, plain paper,
Coated paper (art paper, coated paper, etc.), and in addition to these papers, transparent or opaque plastic film,
And synthetic paper, RC coated with plastic on both sides
Recording paper is used in which an ink receiving layer is provided on various supports (base materials) such as paper.

The ink receiving layer can be roughly divided into a swelling type ink receiving layer mainly composed of polyvinyl alcohol and the like, and a void type ink receiving layer mainly composed of an inorganic fine particle component such as silica.
Void type ink receiving layers, which are excellent in ink absorption rate (drying rate), are becoming mainstream.

Since the void-type ink receiving layer exhibits high ink absorbency because it absorbs ink in the voids, image defects such as beading are unlikely to occur, and the main component is water-insoluble inorganic fine particles. High water resistance.
Also, if the ink receiving layer thickness is set so as to ensure a sufficient ink absorption capacity, the surface will appear to be in a dry state immediately after printing, and it has a drying speed that can be touched or overlapped. There is.

Examples of such a void type ink receiving layer include, for example, JP-A-60-219084, JP-A-63-170074, JP-A-2-43083, and JP-A-4-93284. JP-A-7-1374
No. 31, Japanese Patent Laid-Open No. 8-197832, etc., use various inorganic particles. In addition, the coating liquid (coating liquid) for forming such a void type ink receiving layer on the support is used for reducing the particle size of the inorganic fine particles used for improving the glossiness of the ink receiving layer and for the voids. In order to prevent the ink from being blocked and the ink absorbency being lowered, a low binder content formulation has been performed. On the other hand, the coating film that forms the ink receiving layer becomes fragile, and inorganic fine particles fall off or crack, and a surface with high flatness cannot be formed, resulting in high gloss and clear printed images. Is not obtained, and the mechanical stability of the coating solution is poor, so that there is a problem in production that the contained inorganic fine particle component is precipitated and separated during production.

Further, colloidal silica made of sodium silicate as a raw material is typical as a dispersion of inorganic fine particles in an aqueous solvent. Colloidal silica has extremely high stability because it is manufactured as it is without being dried in a liquid phase and dried, and since it has a small particle size, it is required when high glossiness is required in the above void type ink receiving layer. Has been used. However, due to the production method, the range of use is limited in view of low productivity and economical efficiency, and there is a demand for an inorganic fine particle dispersion liquid which is more economical. Further, when used as an ink receiving layer, it is necessary to form a thick ink receiving layer in order to obtain a sufficient ink absorbency with a small void volume, and the compatibility with an ink fixing agent made of a cationic resin is poor. There is a problem.

Further, as the inorganic fine particles which are excellent in economical efficiency and have a large void volume and a sufficient ink absorbability when used as an ink receiving layer, a dry method produced by a gas phase method using silicon tetrachloride as a raw material. Wet silica, such as silica and precipitated silica and gel silica produced by neutralizing silica and sodium silicate, can be obtained as agglomerated powder, so disperse this in a solvent with good dispersibility. However, the conventional method has a problem that when used as an ink receiving layer, a stable dispersion having a small particle size of 0.5 μm or less that can obtain high gloss cannot be obtained.

[0009]

Therefore, in view of the problems of the prior art, the object of the present invention is to have excellent economical efficiency and liquid stability, and to be excellent in ink absorbability and gloss when used as an ink receiving layer. Another object of the present invention is to provide a composition for inkjet recording, which is capable of forming an image-receiving layer having dryness and water resistance and is capable of obtaining a clear image, and a recording material using the composition.

[0010]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a crosslinkable group-containing cationic acrylic copolymer (A) and a specific cationic resin-modified silica dispersion liquid. The present invention has been completed with an inkjet recording composition comprising (B) and a recording material using the same.

That is, according to the first aspect of the present invention,
A composition for an ink jet recording material which constitutes an image receiving layer formed on at least one surface of a substrate, wherein the composition has a crosslinkable group-containing cationic acrylic copolymer (A) in an amount of 1 to 50 parts by mass, and an average agglomerated particle size. 50-9 silica less than 200 nm
Provided is a composition for an inkjet recording material, which is composed of a cationic resin-modified silica dispersion liquid (B) in an amount of 9 parts by mass. Further, according to the second invention of the present invention, in the first invention, the crosslinkable group-containing cationic acrylic copolymer (A) is a crosslinkable group-containing monomer of 0.1 to 10% by mass, and a cation. Functional group-containing monomer 0.1
99.9 mass% and other monomers 0-99.8 mass%
A composition for an ink jet recording material, which is obtained by copolymerizing the above. Further, according to the third invention of the present invention, in the second invention, the crosslinkable group-containing monomer is a monomer containing an alkoxysilyl group. Will be provided.

According to the fourth aspect of the present invention, the second or third aspect is provided.
In the invention, there is provided a composition for an ink jet recording material, wherein the cationic group-containing monomer is a monomer containing a tertiary amine group and / or a quaternary ammonium salt group. According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the cationic resin-modified silica dispersion liquid (B) is a dispersion obtained by dispersing silica and a cationic resin in a polar solvent. Liquid, light scattering index (n value) when the solid content concentration of the dispersion is 1.5% by mass
Is 2.0 or more, and the composition for inkjet recording bodies is provided. Further, according to a sixth aspect of the present invention, in any one of the first to fifth aspects of the invention, the silica is a silica selected from wet silica or dry silica. Provided.

On the other hand, according to the seventh aspect of the present invention, the first aspect
A recording medium comprising the composition for an inkjet recording medium according to any one of the inventions 1 to 6 is provided.

As described above, the present invention is a composition for an ink jet recording material which constitutes an image receiving layer formed on at least one surface of a base material, wherein the cationic acrylic copolymer copolymer containing 1 to 50 parts by mass of a crosslinkable group is used. A composition for an ink jet recording material, comprising a coalesced (A) and a cationic resin-modified silica dispersion (B) containing an amount of silica having an average aggregate particle diameter of less than 200 nm in an amount of 50 to 99 parts by mass. The present invention relates to a product and the like, and the preferred embodiments thereof include the following.

(1) In the second invention, the cationic group-containing monomer is (meth) acryloyl (CH ₂ ═CHC).
O- or _{CH 2 = C (CH 3)} CO-) inkjet recording-body composition, which is a monomer having a group. (2) In the second invention, the composition for an inkjet recording material is characterized in that the cationic group-containing monomer is diethylaminoethyl (meth) acrylate. (3) In the second invention, the composition for an inkjet recording material is characterized in that the other monomer is (meth) acrylate. (4) In the third invention, the composition for an inkjet recording material is characterized in that the monomer containing an alkoxysilyl group is γ- (meth) acryloxypropyltrimethoxysilane.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The composition for an inkjet recording material (or recording sheet) of the present invention is a composition for an inkjet recording material that constitutes an image receiving layer formed on at least one surface of a substrate, and is 1 to 5
From a cationic resin-modified silica dispersion (B) containing 0 parts by mass of a crosslinkable group-containing cationic acrylic copolymer (A) and 50 to 99 parts by mass of silica having an average aggregate particle size of less than 200 nm. It is characterized by being configured. In the present specification, "acrylic"
The polymerizable monomer and the “methacrylic” polymerizable monomer are collectively referred to as “(meth) acrylic” polymerizable monomer and the like.

1. Crosslinkable Group-Containing Cationic Acrylic Copolymer (A) The crosslinkable group-containing cationic acrylic copolymer (A) is a crosslinkable group-containing monomer of 0.1 to 10% by mass, and a cationic group-containing monomer. It is obtained by copolymerizing 0.1 to 99.9% by mass and 0 to 99.8% by mass of other monomer.

Examples of the cationic group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate and dimethylaminoethyl (meth) acrylate. ) Acrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium sulfate and the like. That is, the cationic group-containing monomer is a monomer containing a tertiary amine group and / or a quaternary ammonium base, and (meth) acryloyl (C
H ₂ = CHCO- or _{CH 2 = C (CH 3)} CO-) is a monomer having a group. Of these, diethylaminoethyl methacrylate is preferable. The monomer having such a cationic group can be used alone or in combination of two or more kinds. In the crosslinkable group-containing cationic acrylic copolymer (A), the content of the cationic group-containing monomer is 0.1 to 99.9% by mass, preferably 0.5 to 30% by mass, and further It is 1 to 10 mass%.

Examples of the crosslinkable group-containing monomer include monomers having an alkoxysilyl group.
Examples of the alkoxysilyl group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane, vinylisobutoxydimethylsilane, and vinyldimethoxymethylsilane. , Vinyldiethoxymethylsilane, vinyltris (β-methoxyethoxy) silane, vinyldiphenylethoxysilane, vinyltriphenoxysilane, γ- (vinylphenylaminopropyl) trimethoxysilane, γ
-(Vinylbenzylaminopropyl) trimethoxysilane, γ- (vinylphenylaminopropyl) triethoxysilane, γ- (vinylbenzylaminopropyl) triethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi (β-methoxyethoxy) ) Silane, vinyldiacetoxymethylsilane, vinyltriacetoxysilane, vinylbis (dimethylamino)
Methylsilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyltrichlorosilane, vinylmethylphenylchlorosilane, allyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, allyldiacetoxymethylsilane, allyltriacetoxysilane, allylbis (dimethylamino) Methylsilane,
Allylmethyldichlorosilane, allyldimethylchlorosilane, allyltrichlorosilane, methallylphenyldichlorosilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxy Propyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyltris Examples include (β-methoxyethoxy) silane. Among them, those having an alkoxysilyl group (C _1-4 alkoxysilyl group such as methoxysilyl group and ethoxysilyl group) are preferable, and γ
-Methacryloxypropyltrimethoxysilane and the like. In the crosslinkable group-containing cationic acrylic copolymer (A), the content of the crosslinkable group-containing monomer is 0.1 to 10
% By mass, preferably 0.5 to 5% by mass, more preferably 1 to 3
It is% by mass.

As the other monomer, the kind of the monomer used is appropriately selected from various known monomers according to the application to which the resin composition is applied. Examples of such a monomer include (meth) acrylic monomers,
Aromatic vinyls, vinyl esters, halogen-containing vinyls, vinyl ethers (eg vinyl ethyl ether etc.), vinyl ketones (eg methyl vinyl ketone etc.), vinyl heterocyclic compounds (eg N-vinyl pyrrolidone, N- Examples thereof include N-vinyl compounds such as vinylimidazole, N-vinylpyridine and the like), olefinic monomers (for example, ethylene and propylene), allyl compounds (for example, allyl esters such as allyl acetate). These monomers may be used alone or in combination of two or more.

The monomeric (meth) acrylic monomers include
For example, (meth) acrylate, (meth) acrylamides, (meth) acrylonitrile and the like are included. Examples of the (meth) acrylate include alkyl (meth) acrylates [eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate. ) Acrylate,
C _1-18 alkyl (meth) acrylate such as t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.], cycloalkyl (Meth) acrylate [eg cyclohexyl (meth) acrylate], aryl (meth) acrylate [eg phenyl (meth) acrylate], aralkyl (meth) acrylate [eg benzyl (meth) acrylate], hydroxyalkyl ( (Meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxy-C _2-4 alkyl (meth) acrylate and the like such as hydroxypropyl (meth) acrylate],
Glycidyl (meth) acrylate, dialkylamino-
Alkyl (meth) acrylate [for example, di-C such as 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, etc.
_1-4 alkylamino-C _2-4 alkyl (meth) acrylate and the like] and the like.

Examples of (meth) acrylamides include:
(Meth) acrylamide, hydroxyalkyl (meth)
Acrylamide [eg N-hydroxy-C _1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide], alkoxyalkyl (meth) acrylamide [N-C ₁ such as N-methoxymethyl (meth) acrylamide, etc.] _-4 alkoxy -C
_1-4 alkyl (meth) acrylamide and the like], diacetoxy (meth) acrylamide and the like are included.

Preferred (meth) acrylic monomers include, for example, (meth) acrylate [eg C
_1-18 alkyl (meth) acrylate, hydroxy-
C _2-4 alkyl (meth) acrylate, glycidyl (meth) acrylate, di C _1-4 alkylamino-C
_2-4 alkyl (meth) acrylate and the like], (meth)
Examples thereof include acrylamides. More preferable (meth) acrylic monomers are C _2-10 alkyl acrylate, C _1-6 alkyl methacrylate, hydroxy-C _2-3 alkyl (meth) acrylate, glycidyl (meth) acrylate, and di C _1-3. Alkylamino- _C2-3 alkyl (meth) acrylate etc. are mentioned.

Aromatic vinyls include, for example, styrene,
It contains α-methylstyrene and vinyltoluene, and styrene is often used. Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl versatate (VeoVa), and the like. The halogen-containing vinyls include, for example, vinyl chloride and vinylidene chloride.

Other monomers are usually hard monomers [for example, monomer components forming a homopolymer having a glass transition temperature of about 80 to 120 ° C. such as methyl (meth) acrylate and styrene] and soft monomers. In many cases, it is used in combination with a monomer [for example, a monomer component that forms a homopolymer having a glass transition temperature of about -85 to 10 ° C, such as acrylic acid C _2-10 alkyl ester]. Methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. are often used. In the crosslinkable group-containing cationic acrylic copolymer (A), the content of the other monomer is 0 to 99.8% by mass, preferably 50 to 99% by mass, and further 80 to 99% by mass. %.
The other monomers may be appropriately 0%, that is, may not be used depending on the types of the crosslinkable group-containing monomer and the cationic group-containing monomer.

In the present invention, the crosslinkable group-containing cationic acrylic copolymer (A) is prepared by copolymerizing a crosslinkable group-containing monomer, a cationic group-containing monomer and other monomers. In this case, various known polymerization methods such as emulsion polymerization can be used. Among them, a method of obtaining a water-based resin composition by removing the solvent used for the solution polymerization after emulsifying the solution by polymerizing each of the copolymerization components and adding water to the obtained resin solution is preferably used. It That is, the above-mentioned respective copolymerization components are mixed and copolymerized in the presence of an appropriate organic solvent, and this polymer is treated with an alkali (for example, alkylamine such as triethylamine, cyclic amine such as morpholine, alkanol such as triethanolamine). Dissolve or disperse using an amine, pyridine, ammonia, etc.) or acid [eg, inorganic acid (eg, hydrochloric acid, sulfuric acid, etc.), organic acid (eg, carboxylic acid such as acetic acid, propionic acid, etc., sulfonic acid, etc.]] . The polymerization operation may be batch type or continuous type.

Examples of the organic solvent used in the solution polymerization include alcohols (eg ethanol, isopropanol, n-butanol etc.) and aromatic hydrocarbons (eg
Benzene, toluene, xylene etc.), aliphatic hydrocarbons (eg pentane, hexane, heptane etc.), alicyclic hydrocarbons (eg cyclohexane etc.), esters (eg ethyl acetate, n-butyl acetate etc.), ketones (For example, acetone, methyl ethyl ketone, etc.), ether (for example, diethyl ether, dioxane, tetrahydrofuran, etc.), etc. can be used. You may use these organic solvents individually or in combination of 2 or more types. The organic solvent is usually an alcohol such as isopropanol, an aromatic hydrocarbon such as toluene,
Ketones such as methyl ethyl ketone are used. The amount of the organic solvent used is not particularly limited, and for example, the amount of the organic solvent with respect to the total amount of the monomers is (0.1 / 1 to 5 /
1), preferably in the range of (0.5 / 1 to 2/1).

In the solution polymerization, the polymerization may be initiated by irradiation with electron beams or ultraviolet rays, but the polymerization is often initiated using a polymerization initiator. Examples of the polymerization initiator include azo compounds [for example, azobisisobutyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, 2,2-azobis (2-amidinopropane) hydro. Chloride, 2,2-azobis (2-amidinopropane) acetate, etc.], inorganic peroxide (for example, potassium persulfate, sodium persulfate,
Persulfates such as ammonium persulfate, hydrogen peroxide), organic peroxides [eg, benzoyl peroxide, di-t-butyl peroxide, cumene hydroxyperoxide,
Di (2-ethoxyethyl) peroxydicarbonate]
And a redox catalyst [eg, sulfite or bisulfite (eg, alkali metal salt, ammonium salt, etc.),
A reducing agent such as L-ascorbic acid or erythorbic acid,
Persulfates (eg, alkali metal salts, ammonium salts, etc.), catalyst systems composed of combinations with oxidizing agents such as peroxides, and the like. The polymerization initiator may be used alone or
A combination of two or more species can be used. The amount of the polymerization initiator used is, for example, 0.001 to 20 with respect to the total weight of the monomers.
% By mass, preferably 0.01-10% by mass (eg
It can be selected from the range of about 0.1 to 10% by mass.

The reaction temperature in the solution polymerization is, for example, 5
It is 0 to 150 ° C., preferably about 70 to 130 ° C. The reaction time is, for example, 1 to 10 hours, preferably 2 to 7 hours. The end point of the polymerization is the absorption of a double bond in the infrared absorption spectrum (1648c
It can be confirmed by the disappearance of m ⁻¹ ), or reduction of unreacted monomers using gas chromatography.

When the polymer contains a cationic group such as an amino group, an imide group or a cation-forming group,
When an acid is used, the hydrophilicity is improved and the polymer can be easily dissolved or emulsified. Examples of such an acid include inorganic acids (eg, hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, etc.), organic acids [eg, saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid; oxalic acid, adipic acid, etc. Saturated aliphatic polycarboxylic acids such as, and unsaturated aliphatic polycarboxylic acids such as (meth) acrylic acid; Unsaturated aliphatic polycarboxylic acids such as maleic acid and itaconic acid; Aliphatic oxycarboxylic acids such as lactic acid and citric acid Etc.] can be exemplified.

The emulsification of the polymer obtained by solution polymerization is
It can be carried out in the presence or absence of an organic solvent. In the presence of an organic solvent, when dissolving or emulsifying and dispersing the polymer,
As the organic solvent, a water-soluble organic solvent (for example, alcohol such as isopropanol) is often used. When the polymer is emulsified in the presence of an organic solvent, the organic solvent may be removed by evaporation after the emulsification, and the emulsion may contain the organic solvent. In addition, when removing an organic solvent before emulsifying a polymer, an organic solvent having a low boiling point (for example, a ketone such as methyl ethyl ketone) is often used.

When the polymer obtained by solution polymerization is emulsified in the presence of an organic solvent, additives (eg emulsifier, pH adjuster, acid, etc.) are added to the organic solution containing the polymer, and then water is added. Can be added to emulsify. In this case, it is preferable to add water gradually by dropping or the like. The temperature at the time of emulsification is preferably low, for example, 5 to 70 ° C,
Preferably, it can be selected from the range of about 10 to 50 ° C. The removal of the organic solvent after addition of water and emulsification is, for example, 5 to
At a temperature of about 80 ° C, under normal pressure or reduced pressure (for example, 0.0
In most cases, it is performed at 001 to 1 atmosphere.

In solution polymerization, in order to adjust the molecular weight of the polymer, a chain transfer agent, for example, alcohols such as catechol, thiols, mercaptans (for example,
n-lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane) and the like may be used.

The average particle size of the polymer particles in the thus obtained aqueous emulsion is in a range that does not impair the dispersion stability, adhesion, etc., for example, 0.01-2 μm,
Preferably 0.01-1 μm, more preferably 0.01
To 0.5 μm, and even more preferably 0.01 to 0.3
It can be selected from the range of about μm.

The crosslinkable group-containing cationic acrylic copolymer (A) according to the present invention may be an aqueous solution or an aqueous emulsion (aqueous polymer emulsion). Such a water-based resin composition is a water-based resin composition that is formed without using a special cross-linking resin such as a cross-linking product of an acrylic silicone oligomer containing a hydrolyzable alkoxysilyl group, and therefore, is easy to handle. Is high. Further, by using this water-based resin composition, it is possible to obtain a coating agent which has little fear of air pollution, poisoning, fire, etc. and has good workability.

Further, the crosslinkable group-containing cationic acrylic copolymer (A) according to the present invention may contain, for example, if necessary,
Add various known additives such as lubricants, antioxidants, UV absorbers, stabilizers such as heat stabilizers, radical scavengers, quenchers, antistatic agents, plasticizers, thickeners, defoamers, etc. May be.

2. Cationic Resin-Modified Silica Dispersion (B) The silica used in the cationic resin-modified silica dispersion (B) according to the present invention is not particularly limited and includes wet silica, dry silica, sol-gel method silica. Any of known silicas such as can be used as a raw material.
The wet silica is typically a precipitated silica formed by neutralizing sodium silicate with a mineral acid to precipitate silica in a solution, which is called white carbon. Similarly, gel method silica produced by neutralizing sodium silicate with an acid can also be used. Furthermore, a dehydrated silica cake that has been filtered and washed only after the neutralization reaction and not subjected to a drying step can also be used.

Further, the above-mentioned dry silica is generally obtained by hydrolyzing silicon tetrachlorides in an oxygen-hydrogen flame at high temperature, and is called fumed silica. The sol-gel method silica is generally obtained by hydrolyzing a silicon alkoxide such as tetramethoxysilane or tetraethoxysilane in an acidic or alkaline water-containing organic solvent. In the present invention, among the above-mentioned silicas, wet silica and dry silica are preferable.

The cationic resin used together with silica is not particularly limited as long as it is a resin that dissociates and exhibits a cationic property when dissolved in water. Among them,
A resin having a primary to tertiary amine or a quaternary ammonium salt is preferably used, and a resin having a quaternary ammonium salt is more preferable.

The polar solvent used in the dispersion is not particularly limited as long as it is a polar solvent in which silica and a cationic resin are easily dispersed. Examples thereof include water; alcohols such as methanol, ethanol and isopropanol; ethers; ketones. Of the above polar solvents, water is preferable, but water and the above polar solvent can be used in combination. In order to improve the stability and dispersibility of the silica particles, a surfactant or the like is added to the cationic resin-modified silica dispersion liquid (B) within a range that does not impair the effects of the present invention.
May be added in a small amount.

The amounts of silica and cationic resin in the cationic resin-modified silica dispersion are not particularly limited,
The amount of silica in the silica dispersion is preferably 8 to 50% by mass, more preferably 8 to 25% by mass, and the amount of the cationic resin is preferably 3 to 50 parts by mass per 100 parts by mass of silica. When the amount of silica in the silica dispersion is more than 50% by mass, the fluidity of the dispersion becomes extremely poor, which makes it difficult to mix. On the other hand, when the amount of silica is less than 8% by mass, a sufficient coating film thickness is obtained during coating. It is not preferable because it is difficult to obtain. When the amount of the cationic resin is less than 3 parts by mass per 100 parts by mass of silica, the surface potential balance of the silica particles becomes non-uniform, and aggregation easily occurs.
On the other hand, when the amount of the cationic resin exceeds 50 parts by mass, the viscosity becomes high and the dispersion treatment becomes difficult.

The silica particles in the cationic resin-modified silica dispersion (B) according to the present invention have a zeta potential as an index of surface charge of +10 mV or more, preferably +20 m.
V or more, and more preferably +30 mV or more. The higher the zeta potential, the more the ink jet image receiving layer,
The fixability of the anionic dye ink is improved. The zeta potential increases as the amount of the cationic resin added increases, but the degree depends on the cationic resin used.

Cationic resin-modified silica dispersion (B)
Means that the average aggregate particle size of silica in the dispersion is 200 nm.
Must be less than 1.5 and the solid content concentration is 1.5
The light scattering index (n value) measured in the dispersion diluted to mass% is preferably 2.0 or more. The particle size of the simple substance of silica is preferably 20 to 30 nm, but is not particularly limited. The n value is an index of the dispersion state of silica in the dispersion liquid, and this value increases as the dispersibility improves. For the n value, the absorbance (τ) is obtained by measuring the spectrum of a silica dispersion liquid having a wavelength (λ) in the range of 460 to 700 nm, and log (λ) and log (τ) are plotted to obtain the following formula (1) ), The slope (-n) of the straight line is obtained by the least square method [ref. Journal of C
erotic Society of Japan 1
01 [6] 707-712 (1993)]. τ = αλ- ⁿ (1)

A specific measurement condition is an optical path length of 10
Using a mm cell, the reference cell and the sample cell are each filled with ion-exchanged water, and 0-point calibration is performed over the wavelength range of 460 to 700 nm. Next, the dispersion is diluted with ion-exchanged water so that the solid content concentration becomes 1.5% by mass, put into a sample cell, and the absorbance in the wavelength range of 460 to 700 nm is measured.

For example, the average aggregate particle size of silica is 200.
When the value is larger than nm and the n value is smaller than 2.0, the ink absorption speed becomes faster, but the smoothness of the ink jet image receiving layer cannot be obtained, the light transmission is hindered, the coating layer becomes opaque, and the gloss is increased. Occurs, which is not preferable.

The method for producing the cationic resin-modified silica dispersion (B) is not particularly limited, and a method in which silica and a cationic resin are simply mixed in a polar solvent, a turbine stator type high speed rotary stirring disperser A method of mixing a silica dispersion and a cationic resin obtained by previously dispersing silica in a polar solvent using a conventional disperser such as a homogenizer or the like, a colloid mill, an ultrasonic emulsifier or the like. , A method of treating a mixture of silica and a cationic resin in a polar solvent using the above-mentioned conventional disperser. Examples of a suitable manufacturing method include a method in which a mixed liquid obtained by mixing silica and a cationic resin in a polar solvent is passed through an orifice under a treatment pressure of 300 kgf / cm ² or more. As such a device, a commercially available device generally called a high pressure homogenizer can be used. As a typical example,
Examples thereof include Nanomizer (manufactured by Nanomizer), Microfluidizer (manufactured by Microfluidics), and Ultimate (manufactured by Sugino Machine).

3. Composition for Inkjet Recording Material In the present invention, the composition for the inkjet recording material (or recording sheet) is compounded by the above-mentioned crosslinkable group-containing cationic acrylic copolymer (A) and cationic resin-modified silica dispersion (B). ). The blending ratio is such that (A) is 1 to 50 parts by mass, (B) is 50 to 99 parts by mass as silica contained in (B), and preferably (A) is 5 to 40 parts by mass. Parts, 60 to 95 parts by mass of silica in (B), more preferably 10 to 30 parts by mass of (A), and 70 to 90 parts by mass of silica in (B). When (A) is 50 parts by mass or more, the ink absorbency is lowered, and when (A) is less than 1 part by mass, the ink image receiving layer is not formed well, or even if it is formed, silica particles are There is a problem in that the powder is remarkably dropped due to falling off from the image receiving layer.

A curing agent (curing catalyst or curing accelerator) may be added to the recording composition of the present invention in order to accelerate the curing reaction. Examples of the curing agent include organic tin compounds (dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, dibutyltin diacetate, dibutyltin dimethoxide, tributyltin sulphite, dibutyltin thioglycolate, tin octylate). Etc.), organoaluminum compounds (aluminum isopropylate, aluminum tris (ethyl acetoacetate),
Aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate, etc.), organic titanium compounds (isopropyl tristearoyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, etc.), organic Zirconium compounds (tetra-n-butoxyzirconium, zirconyl octylate, reaction products of alkoxyzirconium with acetylacetone or acetoacetic acid ester, etc.), acidic compounds (organic acids, for example, acetic acid, aliphatic organic carboxylic acids such as propionic acid, oxy carboxylic acid,
Aromatic carboxylic acids such as benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, sulfonic acids such as dodecylbenzenesulfonic acid, etc., basic compounds (bases such as organic bases such as triethylamine, sodium hydroxide, hydroxylation). Inorganic bases such as potassium), acid phosphates (monobutyl phosphate, dibutyl phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, tridecyl acid phosphate, etc.), said acid phosphate and amine (hexylamine, triethylamine) ,
N, N-dimethyldodecylamine, 3-propanolamine, etc.), a mixture or a reaction product thereof. These curing agents can be used alone or in combination of two or more. The amount of the curing agent used is within a range capable of accelerating the curability, for example, in terms of solid content, 0.0 with respect to 100 parts by mass of the crosslinkable group-containing cationic acrylic copolymer (A).
It is 1 to 10 parts by mass, preferably 0.1 to 5 parts by mass.

Further, in order to improve the fixability of the dye ink, it is advantageous to use a dye fixing agent, particularly a polymer dye fixing agent. The dye fixing agent (polymeric dye fixing agent) usually has a cationic group (particularly, a guanidyl group or a strong quaternary ammonium salt type cationic group) in the molecule. The dye fixative may be water soluble.

Examples of the dye fixing agent include dicyan-based fixing agents (dicyandiamide-formalin polycondensates, etc.), polyamine-based fixing agents [diethylenetriamine, triethylenetetramine, dipropylenetriamine, polyallylamine and other aliphatic polyamines, phenylenediamine, etc.]. Such as aromatic polyamines, condensates of dicyandiamide and (poly) C _2-4 alkylenepolyamines (dicyandiamide-diethylenetriamine polycondensates, etc.)],
Examples thereof include polycationic fixing agents.

Examples of the polycationic fixing agent include, for example,
Epichlorohydrin-diC _1-4 alkylamine addition polymer (epichlorohydrin-dimethylamine addition polymer, etc.), polymer of allylamine or its salt (polymer of polyallylamine or its hydrochloride, for example, Nitto Boseki Co., Ltd., PAA) -10C, PAA-HCl-3L, PA
A-HCl-10L, etc.), a polymer of diallyl C _1-4 alkylamine or a salt thereof (a polymer of diallylmethylamine or a hydrochloride thereof, for example, Nitto Boseki Co., Ltd., PAS
-M-1, etc.), a polymer of diallyldiC _1-4 alkylammonium salt (a polymer of diallyldimethylammonium chloride, for example, Nitto Boseki Co., Ltd., PAS-H-).
5L, PAS-H-10L, etc.), a copolymer of diallylamine or a salt thereof and sulfur dioxide (diallylamine hydrochloride-sulfur dioxide copolymer, for example, PATO-92, Nitto Boseki Co., Ltd.), diallyldiC _{1 -4} alkylammonium salt-sulfur dioxide copolymer (diallyldimethylammonium chloride-sulfur dioxide copolymer, for example, Nitto Boseki Co., Ltd., PAS-A-1, PAS
-A-5, PAS-A-120L, PAS-A-120
A), a copolymer of diallyldiC _1-4 alkylammonium salt and diallylamine or a salt or derivative thereof (a copolymer of diallyldimethylammonium chloride-diallylamine hydrochloride derivative, for example, Nitto Boseki Co., Ltd., PAS-880). etc.), Jiariruji _{C 1-4} alkylammonium salt polymers, polymers of _{di-C 1-4} alkylamino ethyl (meth) acrylate quaternary salt, Jiariruji _{C 1-4} alkylammonium salt - acrylamide copolymer (diallyldimethylammonium Chloride-
Acrylamide copolymer, for example, Nitto Boseki Co., Ltd., P
AS-J-81), amine-carboxylic acid copolymers (eg, Nitto Boseki Co., Ltd., PAS-410, etc.) and the like. These dye fixing agents can be used alone or in admixture of two or more.

The amount of the dye fixing agent used is in the range capable of improving the fixability, for example, 0.1 to 4 based on 100 parts by mass of the crosslinkable group-containing cationic acrylic copolymer in terms of solid content.
It can be selected from the range of 0 parts by mass, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass.

In the image-receiving layer, if necessary, other components, for example, an aqueous emulsion containing a polymer having no crosslinkable group or polymer particles (eg, acrylic resin emulsion, ethylene-vinyl acetate copolymer). Combined emulsion, vinyl acetate emulsion, etc.) may be contained.

The ink absorbing layer may contain a powder or granular material (such as a pigment). As the granular material, for example, inorganic granular material (white carbon, particulate calcium silicate, zeolite, magnesium aminosilicate, calcined diatomaceous earth, particulate magnesium carbonate, particulate alumina, silica, talc, kaolin, deramikarin, clay, Mineral powders such as heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium silicate, calcium sulfate, sericite, bentonite, smectite, etc.), organic Examples thereof include powder particles (crosslinked or non-crosslinked organic fine particles such as polystyrene resin, acrylic resin, urea resin, melamine resin and benzoguanamine resin, organic powder particles such as fine hollow particles). These powders can be used alone or in combination of two or more as appropriate. In addition, when using a granular material, the said hydrophilic polymer can be used as a binder resin. The ratio of the powder and granules to the binder resin is, for example, about 0.1 to 80 parts by mass, preferably about 0.2 to 50 mass parts, relative to 100 parts by mass of the binder resin.

Further, conventional additives such as antifoaming agents, coating improvers, thickeners, lubricants,
Stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.),
You may add an antistatic agent, an anti-blocking agent, etc.

As a method for blending the composition for an ink jet recording material of the present invention, a conventional apparatus can be used. For example, a method of simply mixing using a stirring blade, a turbine stator type high speed rotary stirring / dispersing machine (eg, homogenizer, etc.), a colloid mill, an ultrasonic emulsifier, a high pressure homogenizer, etc. The method of doing is mentioned.

4. Substrate In the present invention, the substrate on which the image receiving layer (or recording layer) is formed on at least one surface may be opaque, semitransparent or transparent depending on the application, and is used in an overhead projector (OHP) or the like. The substrate is usually transparent. The material of the substrate is not particularly limited, and examples of usable substrates include paper, coated paper, non-woven fabric, plastic film, and synthetic paper.

Examples of the polymer constituting the plastic film and the synthetic paper include polyolefin such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, poly (meth) acrylic. Acid ester, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivatives such as cellulose acetate,
Polyesters (polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate), polycarbonates, polyamides (polyamide 6, polyamide 6)
/ 6, polyamide 6/10, polyamide 6/12, etc.), polyester amides, polyethers, polyimides, polyimide amides, polyether esters, and the like. Further, using copolymers, blends, and crosslinked products of these Good.

Polyolefins (especially polypropylene), polyesters (especially polyethylene terephthalate, etc.), polyamides, etc. are usually used as polymers constituting these plastic films or synthetic papers, and in particular mechanical strength, workability, cost, etc. From the viewpoint of, polyester (particularly polyethylene terephthalate) is preferable. As the paper or coated paper, for example, high-quality paper, art paper, RC paper or the like can be used.

The thickness of the base material can be selected according to the application and is usually 5 to 500 μm, preferably about 10 to 300 μm. The base material may have a sizing agent, an antioxidant, an ultraviolet absorber, a heat stabilizer, or an internal or surface thereof, if necessary.
Conventional additives such as lubricants and pigments may be used. In addition, surface treatment such as corona discharge treatment or undercoat treatment may be performed in order to improve the adhesiveness to the image receiving layer.

5. Method for Producing Recording Body The recording body (or recording sheet) of the present invention can be produced by forming an image receiving layer made of the composition for recording body on at least one surface of the substrate. For each image-receiving layer, a coating liquid prepared by using an appropriate solvent (water, a hydrophilic solvent which may be water-soluble, a hydrophobic solvent or a mixed solvent thereof) is applied to a support (base material). Can be formed by.

The coating solution is applied to the substrate by a conventional casting or coating method, for example, a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, a gravure coater, a silk screen coater method. At least one surface is cast or coated.

The image-receiving layer can be formed by applying a coating solution containing the above-mentioned components on at least one surface of the substrate and drying. If necessary, after applying the coating liquid, 5
The crosslinked ink absorbing layer may be formed by heating at an appropriate temperature selected from the range of about 0 to 150 ° C. In addition,
If necessary, a porous layer, an antiblocking layer, a slipping layer, an antistatic layer or the like may be formed on the image receiving layer. The thickness of the image-receiving layer formed by the composition for a recording medium can be selected according to the application and is, for example, 3 to 50 μm, preferably 6 to 30 μm, and usually about 5 to 30 μm.

The recording medium of the present invention is useful as a recording sheet by an ink jet system for recording by ejecting small droplets of ink, but printing sheets for offset printing, flexographic printing, etc. (especially water-based ink sheets), etc. Also available as

[0065]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. All parts are parts by mass.

[Crosslinkable group-containing cationic acrylic copolymer aqueous dispersion (A-1)] Isopropanol 48 was placed in a 2000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introducing tube and a thermometer. And 0.25 parts of azoisobutyronitrile were added, and the mixture was stirred and dissolved, and heated to 80 ° C. As a copolymerization component, methyl methacrylate 36
Parts, n-butyl acrylate 11 parts, diethylaminoethyl methacrylate 2 parts, and trimethoxysilane propyl methacrylate (manufactured by Nippon Unicar Co., Ltd., A-1).
74) 1.5 parts were mixed and added dropwise into the flask over about 4 hours. After completion of the dropping, a solution of 0.2 part of azoisobutyronitrile and 2 parts of isopropanol was added dropwise as an additional catalyst, and the reaction was continued for another 2 hours to complete the polymerization.
After completion of the polymerization, while continuing stirring, 0.6 part of formic acid was added to the flask, 160 parts of water was added dropwise over about 1 hour, and then isopropanol was evaporated by a rotary evaporator to obtain a crosslinkable group-containing cationic acrylic system. An aqueous copolymer dispersion (A-1) was obtained. The properties of the obtained copolymer aqueous dispersion (A-1) are such that the nonvolatile content is 30% by mass and the viscosity is 1
It was 00 mPa · s @ 23 ° C.

[Crosslinkable Group-Containing Anionic Acrylic Copolymer Aqueous Dispersion (A-2)] In the copolymer (A-1),
The composition of the monomer to be polymerized was 2 parts of acrylic acid instead of 2 parts of diethylaminoethyl methacrylate, and 2 parts of ammonia water (25% by mass) was added to the flask instead of 0.6 part of formic acid added after the completion of the polymerization. Was changed and synthesized in the same manner. The properties of the obtained copolymer aqueous dispersion (A-2) are such that the nonvolatile content is 30% by mass and the viscosity is 3
It was 0 mPa · s @ 23 ° C.

[Aqueous dispersion of crosslinkable group-free cationic acrylic copolymer (A-3)] Trimethoxysilanepropyl methacrylate (manufactured by Nippon Unicar Co., Ltd., A-174)
A copolymer aqueous dispersion (A-3) was synthesized in the same manner as the copolymer aqueous dispersion (A-1) except that was not used. The obtained copolymer aqueous dispersion (A-3) had a nonvolatile content of 30.
The mass% and the viscosity were 80 mPa · s @ 23 ° C.

[Cationic Resin-Modified Silica Dispersion (B)] Commercially available sodium silicate and pure water were charged in a reaction tank so that a solution having a sodium silicate concentration of 5% by mass was formed. This solution was heated at 40 ° C. for 1 hour, and a neutralization reaction was performed with 22 mass% sulfuric acid to a neutralization rate of 50%, and then the temperature of the reaction solution was raised to 95 ° C. The reaction solution has a neutralization rate of 1
The sulfuric acid was added until it was 00%. The produced silica was repeatedly filtered and washed to obtain a dehydrated cake (silica content: 15% by mass). The specific surface area of silica obtained by drying this dehydrated cake is 280 m ² /
It was g. 2000 g of this dehydrated cake and 500 g of pure water
Was added and premixed by stirring with a propeller mixer to obtain a silica slurry. The obtained silica slurry was treated with a high pressure homogenizer (Nanomizer, Nanomizer, LA-31) at a processing pressure of 800 kgf /
The powder was passed through the orifice 3 times at cm ² to obtain a pulverized silica dispersion liquid. In 1000 g of this pulverized silica dispersion liquid, as a cationic resin, an aqueous solution of diallyldimethylammonium chloride-acrylamide copolymer having a concentration of 25 mass% 48
g was added, and a premixed liquid was obtained with a propeller mixer. The resulting premixed liquid was passed through the orifice twice at a processing pressure of 800 kgf / cm ² using a high pressure homogenizer (Nanomizer, Nanomizer, LA-31) to give the cationic resin-modified silica dispersion (B). Obtained. The properties of the resulting silica dispersion (B) are
Nonvolatile content 12.6% by mass (11.5% by mass as silica), n value 2.5, viscosity 50 mPa · s @ 23 ° C.,
Average aggregate particle size 140nm, Zeta potential + 40mV
Met.

[Example 1] 800 parts of a cationic resin-modified silica dispersion (B) per 100 parts of the aqueous dispersion of a crosslinkable group-containing cationic acrylic copolymer (A-1) (30 parts as resin content). (92 parts as silica) was mixed to obtain a coating liquid having a nonvolatile content of 17% by mass. The compounding ratio of the crosslinkable group-containing cationic acrylic copolymer and silica was 24.6.
The volume was 75.4. Then, the above-mentioned coating liquid was applied to a polyethylene terephthalate film having a thickness of 100 μm and subjected to an easy-adhesion treatment (DuPont Melinex 705, which may hereinafter be simply referred to as a PET film), and the coating solution was applied at 105 ° C.
By drying for minutes, an ink receiving layer (image receiving layer) having a coating amount of 22 g / m ² was formed, and a recording sheet 1 was obtained.

Example 2 Crosslinkable group-containing cationic activator
100 parts of ril copolymer aqueous dispersion (A-1) (as resin content
30 parts) to a cationic resin-modified silica dispersion
(B) 300 parts (34.5 parts as silica) are blended
Thus, a coating liquid having a nonvolatile content of 19% by mass was obtained. Crosslinkable group included
The compounding ratio of the cationic acrylic copolymer and silica is 4
It was 6.5 parts to 53.5 parts. Coating as in Example 1
Application amount by drying cloth, 23g / m ^TwoInk receiver
Then, a recording layer 2 was obtained.

[Comparative Example 1] Acid-type colloidal silica ST-AK (manufactured by NISSAN CHEMICAL CO., INC., Silica content: 20% by mass) based on 100 parts of the crosslinkable group-containing cationic acrylic copolymer aqueous dispersion (A-1). ) 450 parts were blended to obtain a coating liquid having a nonvolatile content of 22% by mass. By coating and drying in the same manner as in Example 1, an ink receiving layer having a coating amount of 29 g / m ² was formed, and a recording sheet 3 was obtained.

[Comparative Example 2] 450 parts of colloidal silica ST-20 (manufactured by NISSAN CHEMICAL CO., LTD., Silica content 20% by mass) with respect to 100 parts of the aqueous dispersion of anionic acrylic copolymer containing a crosslinkable group (A-2). 22 parts by mass of non-volatile content
The coating liquid was obtained and applied and dried in the same manner as in Example 1 to form an ink receiving layer with a coating amount of 29 g / m ² , and a recording sheet 4 was obtained.

[Comparative Example 3] With respect to 100 parts of the aqueous dispersion of the cationic acrylic copolymer (A-3) containing no crosslinkable group,
800 parts of the cationic resin-modified silica dispersion liquid (B) was mixed to obtain a coating liquid having a nonvolatile content of 17% by mass. Example 1
22 g / m ² by applying and drying in the same manner as
The ink receiving layer of was formed to obtain a recording sheet 5.

[Comparative Example 4] The cationic resin-modified silica dispersion (B) was applied alone, and coated and dried in the same manner as in Example 1 to form an ink receiving layer having a coating amount of 20 g / m ² . Recording sheet 6 was obtained.

[Evaluation Method and Evaluation Criteria] An ink jet printer (PM-800C manufactured by Seiko Epson Corp.) is used, and a color pattern composed of each color of cyan, yellow, magenta and black is formed on the recording sheets 1 to 6. Was printed with a paper setting of photo print paper to form a recorded image. The results obtained on each recording sheet are shown in Table 1. The evaluation items and criteria are as follows.

[Ink Absorption] The printed image was visually observed and evaluated according to the following criteria. ◯: No bleeding is visually observed. Δ: A slight blur is visually observed. X: Image bleeding is remarkable.

[Ink Fixability] Solid print portions of each color (cyan, yellow, magenta, black) were immersed in ion-exchanged water for 1 hour, and the image was visually observed according to the following criteria. ◯: No change is visually observed ×: Image is clearly thinned or ink is flowing visually.

[Ink Dryability] For each solid print portion of each color (cyan, yellow, magenta, black), after a predetermined time from the end of printing, the PPC paper is pressed and the time until the ink is not transferred to the PPC paper side is measured. did.

[60 ° Gloss] The 60 ° gloss of the unprinted portion was measured.

[Pencil Strength] The unprinted portion is JISK540
It was measured according to 0 and evaluated by the breakage of the coating film.

[0082]

[Table 1]

As can be seen from Table 1, the recording sheets obtained in Examples 1 and 2 are different from Comparative Examples 1 to 4 in ink absorbency, ink fixability, ink dryness, gloss of coating film, and It was found that the coating film strength was excellent.

[0084]

INDUSTRIAL APPLICABILITY The composition for ink jet recording material of the present invention has an average aggregate particle diameter of 200 nm obtained by aggregating silica particles.
The amount of the cationic resin-modified silica dispersion is less than the above, and a recording material using the same can have high gloss while having high ink absorbing ability and ink fixability.

Continued front page    F-term (reference) 2C056 EA13 FC06                 2H086 BA01 BA15 BA33 BA34 BA41                 4J038 CG141 CG211 CH201 CH261                       EA011 GA08 GA09 GA15                       HA446 KA08 KA20 MA07                       MA10 NA01 NA04 NA18 NA24                       NA25 PB11                 4J039 AD10 BA21 BE12 CA07 EA10                       EA33 EA38 EA44 GA24

Claims (7)

[Claims] 1. A composition for an ink jet recording material, which constitutes an image receiving layer formed on at least one surface of a substrate, comprising:
A cationic resin-modified silica dispersion liquid (B) containing 1 to 50 parts by mass of a crosslinkable group-containing cationic acrylic copolymer (A) and 50 to 99 parts by mass of silica having an average aggregate particle diameter of less than 200 nm. And a composition for an ink jet recording material. 2. The crosslinkable group-containing cationic acrylic copolymer (A) is a crosslinkable group-containing monomer in an amount of 0.1 to 10% by mass,
The inkjet recording according to claim 1, which is obtained by copolymerizing 0.1 to 99.9% by mass of a cationic group-containing monomer and 0 to 99.8% by mass of another monomer. Body composition. 3. The crosslinkable group-containing monomer is a monomer containing an alkoxysilyl group.
The composition for inkjet recording material according to item 1. 4. The ink jet recording material according to claim 2, wherein the cationic group-containing monomer is a monomer containing a tertiary amine group and / or a quaternary ammonium salt group. Composition. 5. A cationic resin-modified silica dispersion (B)
Is a dispersion liquid in which silica and a cationic resin are dispersed in a polar solvent, and the solid content concentration of the dispersion liquid is 1.5.
The light scattering index (n value) in mass% is 2.0 or more, and the composition for inkjet recording material according to any one of claims 1 to 4. 6. The silica according to claim 1, wherein the silica is selected from wet silica and dry silica.
The composition for inkjet recording material according to any one of 1. 7. A recording material comprising the composition for inkjet recording material according to claim 1.