JP2002096552A - Resin composition for ink jet recording, and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for ink jet recording which has properties of drying (absorbing) ink, a coat strength preventing falling-off of inorganic particulates and cracking, a printed image quality of a high degree and glossiness, and an ink jet recording material using the same. SOLUTION: The resin composition for ink jet recording contains the inorganic particulates of 50-2,000 pts.wt. to 100 pts.wt. of an acrylic resin having a hydrolyzable silyl group, and the ink jet recording material has at least one layer of the resin composition as an ink receiving layer on a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for ink jet recording and a recording material, and more particularly, to a high ink drying property (absorbency), a coating strength and a high coating strength that do not cause inorganic fine particles to fall off or crack. The present invention relates to a resin composition for ink jet recording having excellent print quality and gloss and an ink jet recording material having a void phase formed from the resin composition as an ink receiving layer on a substrate.

[0002]

2. Description of the Related Art Ink jet recording systems have been rapidly spreading in recent years because they are inexpensive, can be easily made full color, have low noise, and have excellent print quality. In the inkjet recording, a water-based ink is mainly used from the viewpoint of safety and recording suitability, and recording is performed by flying small ink droplets from a nozzle toward a recording sheet. Therefore, the recording sheet is required to quickly absorb the ink. That is, in a recording sheet having a low ink absorbency, the ink remains on the surface of the recording sheet for a long time even after the recording is completed, and the recording is performed due to contact with a part of the apparatus, contact of a handler, or superposition of the recording sheet. The part gets dirty. In the high-density image portion, a large amount of supplied ink is mixed and flows out without being absorbed, resulting in an unclear image.

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

As the ink receiving layer, a so-called swelling type ink receiving layer mainly composed of a water-soluble or hydrophilic resin such as polyvinyl alcohol, and a void layer mainly formed of a fine particle component such as silica are used. , A so-called void type ink receiving layer. As these ink receiving layers, for example, JP-A-63
Japanese Patent Application Laid-Open No. 115780/1999 contains synthetic silica (meth)
A polymer having a skeleton of an alkyl acrylate quaternary ammonium salt and / or a (meth) acrylamidoalkyl quaternary ammonium salt is disclosed in JP-A-6-227114. A pigment containing fine silica and a zwitterionic latex are mainly used. And those formed from aqueous compositions.

[0005] An ink jet recording material having a swelling type ink receiving layer has a silver salt of extremely high gloss and color density after the ink solvent composed of water and a high-boiling organic solvent (such as glycerin or ethylene glycol) is completely evaporated. This has the advantage that an image having a photographic feel can be obtained, but the ink absorption rate (drying rate) is slower than that of the void type ink receiving layer, and in some cases, several hours after printing due to the effect of the high boiling point solvent in the ink solvent The ink receiving layer remains swollen and wet for several days from the beginning, and has a disadvantage that it cannot be sticky or overlapped. In addition, in a portion where the amount of printing ink is large, there is a problem that an image defect such as beading occurs due to insufficient ink absorbency, and it is difficult to achieve both ink absorbency and water resistance. In particular, as the image quality increases, such as by increasing the speed of the printer, using photo ink, and printing at a high resolution of 1000 dpi or more, the ink absorption speed (drying speed) becomes a problem.

On the other hand, an ink jet recording material having a void type ink receiving layer exhibits high ink absorbency because the voids absorb ink. For this reason, image defects such as beading are unlikely to occur, and the water resistance is high because of using water-insoluble inorganic fine particles as a main component. In addition, if the thickness of the ink receiving layer is set so that sufficient ink absorption capacity can be secured, even if the ink solvent such as a high boiling point organic solvent remains in the voids, the surface is apparently dry immediately after printing. And has a drying rate that can be touched and overlapped. However, despite such advantages, there is a problem that gloss is too low due to the presence of voids.

The above-mentioned void-type ink receiving layer is described in, for example, JP-A-60-219084 and JP-A-63-1.
7,0074, JP-A-2-43083, JP-A-4-9328
4, No. 7, 137431, and No. 8-197832, which disclose various inorganic particles. An ink jet recording medium having such a gap type ink receiving layer on a substrate has high ink absorbency, and improvement in glossiness has been promoted. However,
If the content of the binder with respect to the inorganic fine particles is too large to increase the gloss, the voids formed between the inorganic fine particles may be closed, or depending on the properties of the binder resin, the binder resin swells due to the ink solvent and the voids are formed. There is a problem that the ink cannot be sufficiently absorbed due to blocking. On the other hand, if the ratio of the inorganic fine particles is excessively increased in order to secure the ink absorbency and the absorption capacity, the strength of the coating film forming the ink receiving layer is reduced and becomes brittle, and the inorganic fine particles may fall off or crack. And the surface having high flatness cannot be formed. This tendency becomes more pronounced when trying to form a thick ink receiving layer. There is also a problem that the adhesion between the ink receiving layer and the substrate is deteriorated. Therefore, development of a resin composition for ink jet recording, which has a high ink absorption rate and excellent coating film strength, print quality and gloss, and a recording material using the same have been demanded.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording which has both the drying property (absorbing property) of the ink, the strength of the coating film which does not cause the removal of inorganic fine particles or cracks, the high printing quality and the gloss. And a recording material using the same.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a resin composition containing an acrylic resin having a hydrolyzable silyl group and inorganic fine particles at a specific ratio. It has been found that this problem can be solved by using a recording material in which at least one ink-receiving layer is formed on a base material as a void layer made of the resin composition, thereby completing the present invention.

That is, according to the first aspect of the present invention,
Acrylic resin (a) 100 having a hydrolyzable silyl group
There is provided an ink jet recording resin composition containing 50 to 2,000 parts by weight of inorganic fine particles (b) based on part by weight.

According to the second aspect of the present invention, the first aspect is provided.
The acrylic resin (a) having a hydrolyzable silyl group in the invention of (1) is a polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon crosslinks of 0.5 to 50% by weight.
And 1 to 20% by weight of a polymerizable unsaturated monomer (B) having at least one ion-forming group and another polymerizable unsaturated monomer (D) Ｄ100-((A) + (B ))｝
And a resin composition for ink-jet recording, which is a copolymer obtained by copolymerizing the resin composition with an ink composition of the present invention.

Further, according to the third invention of the present invention, the acrylic resin (a) having a hydrolyzable silyl group in the first invention is a polymerizable polymer having a long hydrolyzable silyl group between silicon bridges. 0.5 to 50% by weight of a saturated monomer (A), 1 to 20% by weight of a polymerizable unsaturated monomer (B) having at least one ion-forming group, and the following general formula (1) 5 to 20% by weight of a monomer (C) containing an alkylene oxide unit represented and another polymerizable unsaturated monomer (D) @ 100-((A) + (B) +
(C)) a resin composition for inkjet recording, which is a copolymer obtained by copolymerizing｝% by weight.

Embedded image (Wherein, R ¹ represents a hydrogen atom, a methyl group or a hydroxyl group, R ² represents a hydrogen atom or a methyl group, and n represents 1 to 5
And m represents an integer of 1 to 20. )

According to the fourth aspect of the present invention, the first aspect is provided.
The acrylic resin (a) having a hydrolyzable silyl group in the invention of the invention is an aqueous resin composition obtained by adding water to a resin solution obtained by solution polymerization, emulsifying the resin solution, and then removing the polymerization solvent. An ink-jet recording resin composition is provided.

Further, according to the fifth aspect of the present invention, the second aspect
Alternatively, the resin composition for inkjet recording, wherein the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon crosslinks in the third invention is represented by the following general formula (2) is provided. .

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ ,
R ⁵ represents an alkyl group, an aryl group, an aralkyl group, an alkoxyl group, an aryloxy group, a hydroxyl group or an alkylthio group which may be the same or different; X represents a halogen atom; r is an integer of 1 to 20; 0-2
Indicates an integer. )

Further, according to a sixth aspect of the present invention, the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon bridges in the second or third aspect is
An inkjet recording resin composition represented by the following general formula (3) is provided.

Embedded image (Wherein, R ⁶ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and R ⁹ is a hydrogen or 1 to 10 carbon atoms.
10 alkyl groups, aryl groups or aralkyl groups, X
Is a hydrolyzable group selected from the group consisting of halogen, alkoxy, acyloxy, ketoximate, amino, acid amide, aminooxy, mercapto and alkenyloxy groups, o + p is 2 or more, and o and p are 0 to 100.
And q represents an integer of 0 to 2. )

According to the seventh aspect of the present invention, the first aspect is provided.
The present invention provides an aqueous resin composition having an average particle diameter of the acrylic resin (a) having a hydrolyzable silyl group of 0.01 to 0.1 [mu] m.

According to the eighth aspect of the present invention, the first aspect is provided.
The average particle diameter of the inorganic fine particles (b) according to the invention is 1 to 5
A resin composition for inkjet recording having a thickness of 00 nm is provided.

According to the ninth aspect of the present invention, the first aspect
The present invention provides a resin composition for inkjet recording, wherein the inorganic fine particles (b) are colloidal silica.

Further, according to a tenth aspect of the present invention,
There is provided an ink jet recording material having at least one void layer formed from the resin composition according to the first to ninth aspects as an ink receiving layer on a substrate.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to preferred embodiments. (A) Acrylic resin having hydrolyzable silyl group As the acrylic resin having a hydrolyzable silyl group (a) of the present invention, a polymerizable unsaturated monomer having a hydrolyzable silyl group is polymerized or copolymerized. Use things. Examples of the polymerizable unsaturated monomer having a hydrolyzable silyl group include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane,
Vinylisobutoxydimethylsilane, 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, Allylphenyldichlorosilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltri Ethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyltris (β -Methoxyethoxy) silane and the like. Preferably, it is a polymerizable unsaturated compound having an alkoxysilyl group (a _C1-4 alkoxysilyl group such as a methoxysilyl group and an ethoxysilyl group).

In particular, as the acrylic resin (a) having a hydrolyzable silyl group, a polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon crosslinks and at least one kind of ion-forming monomer. Polymerizable unsaturated monomer (B) having a functional group and other polymerizable unsaturated monomer (D)
Or a monomer containing an alkylene oxide unit represented by the following general formula (1) in addition to the above-mentioned monomers (A), (B) and (D). It is preferable to use a copolymer obtained by copolymerizing the monomer (C).

Embedded image (Wherein, R ¹ represents a hydrogen atom, a methyl group or a hydroxyl group, R ² represents a hydrogen atom or a methyl group, and n represents 1 to 5
And m represents an integer of 1 to 20. )

By using the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between the silicon bridges as a copolymer component, the silyl group acts as a crosslinkable functional group at the time of coating film formation. In addition, the coating film has an appropriate elasticity and can improve the coating film strength and the like. Examples of the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between the silicon bridges include a polymerizable unsaturated monomer containing a silyl group represented by the following general formula (2). No.

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ ,
R ⁵ represents an alkyl group, an aryl group, an aralkyl group, an alkoxyl group, an aryloxy group, a hydroxyl group or an alkylthio group which may be the same or different; X represents a halogen atom; r is an integer of 1 to 20; 0-2
Indicates an integer. )

The halogen atom bonded to the silyl group represented by the formula (2) includes, for example, fluorine, chlorine, bromine and iodine, and is usually a chlorine atom. The alkyl group, e.g., methyl, ethyl, propyl, butyl, pentyl, and the like C _{1 -10} alkyl groups such as hexyl group. Here, C _1-10 means “1 to 1 carbon atoms”.
10 "and the same applies hereinafter.
Aryl groups, e.g., C _{6 -10} such as a phenyl group
Aryl groups and the like are included, and aralkyl groups include, for example,
Such as C _{7 -10} aralkyl groups such as benzyl groups include.

Alkoxyl groups include, for example, methoxy,
Ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, and the like C _{1 -16} alkoxy groups such as dodecyloxy group.
Preferred alkoxyl groups are C _1-4 alkoxyl groups,
Particularly, it is a methoxy group or an ethoxy group. The alkoxyl group also includes, for example, an alkoxy-substituted alkoxyl group such as a methoxyethoxy group.

[0025] The aryloxy groups include, for example, such as C _{6 -10} aryloxy group such as phenoxy group. The acyloxy group includes, for example, a C _1-6 acyloxy group such as acetyloxy, propionyloxy, and butyryloxy group.

Examples of such compounds include trimethoxysilylpropyl isocyanate-modified Praxel FM3, triethoxysilylpropyl isocyanate-modified Praxel FM3, and the like. Here, trimethoxysilylpropyl isocyanate-modified Praxel FM
3 is Praxel FM3 manufactured by Daicel Chemical Industries, Ltd.
(Compound obtained by addition polymerization of ε-caprolactone to the OH group of hydroxyethyl methacrylate)
A compound obtained by urethane reaction of isocyanatepropyltrimethoxysilane (Y-5187 manufactured by Nippon Unicar Co., Ltd.) and triethoxysilylpropyl isocyanate-modified Praxel FM3 are manufactured by Daicel Chemical Industries, Ltd. and Plaxel FM3 (hydroxyethyl methacrylate). O
A compound obtained by subjecting a terminal OH group of an H group to addition polymerization of ε-caprolactone) to a urethane reaction between γ-isocyanatopropyltriethoxysilane (A-1310, manufactured by Nippon Unicar Co., Ltd.).

Further, as another polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon bridges,
For example, a polymerizable unsaturated monomer containing a silyl group represented by the following general formula (3) may be mentioned.

Embedded image (Wherein, R ⁶ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and R ⁹ is a hydrogen or 1 to 10 carbon atoms.
10 alkyl groups, aryl groups or aralkyl groups, X
Is a hydrolyzable group selected from the group consisting of halogen, alkoxy, acyloxy, ketoximate, amino, acid amide, aminooxy, mercapto and alkenyloxy groups, o + p is 2 or more, and o and p are 0 to 100.
And q represents an integer of 0 to 2. )

C bonded to the silyl group represented by the formula (3)
For example, fluorine, chlorine, bromine, iodine
Etc., which are usually chlorine atoms. To the alkyl group
Is, for example, methyl, ethyl, propyl, butyl, pen
C such as tyl and hexyl groups_{1- 10}Including alkyl groups
I will. Aryl groups include, for example, C
_6-10Aryl groups and the like are included, and aralkyl groups include
For example, C such as a benzyl group_7-10Aralkyl groups, etc.
Is included.

The alkoxyl group includes, for example, methoxy,
Ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, and the like C _{1 -16} alkoxy groups such as dodecyloxy group.
Preferred alkoxyl groups are C _1-4 alkoxyl groups,
Particularly, it is a methoxy group or an ethoxy group. The alkoxyl group also includes, for example, an alkoxy-substituted alkoxyl group such as a methoxyethoxy group.

[0030] The aryloxy groups include, for example, such as C _{6 -10} aryloxy group such as phenoxy group. The acyloxy group includes, for example, a C _1-6 acyloxy group such as acetyloxy, propionyloxy, and butyryloxy group.

Examples of such a compound include trimethoxysilylpropyl isocyanate-modified prenemer PE-200, triethoxysilylpropyl isocyanate-modified prenemer PE-200, and the like. Here, trimethoxysilylpropyl isocyanate-modified prenemer PE-200 is polyethylene glycol monomethacrylate (manufactured by NOF Corporation, prenemer PE
-200) and γ-isocyanatopropyltrimethoxysilane (Y-51, manufactured by Nippon Unicar Co., Ltd.)
87), a compound obtained by a urethane reaction of triethoxysilylpropyl isocyanate-modified prenemer PE-200
Is the terminal OH of polyethylene glycol monomethacrylate (Plenmer PE-200, manufactured by NOF Corporation)
It is a compound obtained by subjecting a group to γ-isocyanatopropyltriethoxysilane (A-1310, manufactured by Nippon Unicar Co., Ltd.) through a urethane reaction.

The polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon bridges can be used alone or
It can be used in combination of more than one kind. Desirable silyl group-containing monomers (A) include, for example, triethoxysilylpropyl isocyanate-modified Praxel FM3 and triethoxysilylpropyl isocyanate-modified prenemer PE-200 from the viewpoints of handleability, economy and suppression of side reactions. No.

The acrylic resin (a) having a hydrolyzable silyl group preferably contains a polymerizable unsaturated monomer (B) having at least one ion-forming group as a copolymerization component of the resin. Used. By using this monomer (B) as a component for copolymerization, the resulting polymer has an ion-forming group, and the polymer can be easily emulsified.

Examples of the ion-forming group include a cation-forming group such as an amino group and an imino group, and an anion-forming group such as a carboxyl group. Examples of the polymerizable unsaturated monomer (B) having a cation-forming group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate Dimethylaminoethyl (meth) acrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium sulfate, and the like. Such monomers having a cation-forming group (B) can be used alone or in combination of two or more.

Examples of the polymerizable unsaturated monomer (B) having an anion-forming group include carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, vinyl carboxylic acid [(meth) acrylic acid, crotonic acid , Sorbic acid, maleic acid, itaconic acid, cinnamic acid, etc.], vinyl sulfonic acid [vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene ene sulfonic acid, styrene sulfonic acid, etc.], (meth) acryl sulfonic acid [(meth) Sulfoethyl acrylate, sulfopropyl (meth) acrylate], (meth) acrylamidosulfonic acid [2-acrylamido-2-methylpropanesulfonic acid, etc.]. These monomers (B) having an anion-forming group can be used alone or in combination of two or more.

In the acrylic resin (a) having a hydrolyzable silyl group, another polymerizable unsaturated monomer (D) is preferably used as a copolymer component of the resin.
The polymerizable unsaturated monomer (D) is appropriately selected from known polymerizable unsaturated monomers according to the application to which the resin composition is applied.

Examples of such a polymerizable unsaturated monomer (D) include (meth) acrylic monomers, aromatic vinyls, vinyl esters, halogen-containing vinyls, and vinyl ethers (for example, vinyl Ethyl ether),
Vinyl ketones (for example, methyl vinyl ketone, etc.),
Vinyl heterocyclic compounds (for example, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylimidazole;
N-vinylpyridine and the like; olefin-based monomers (eg, ethylene and propylene); allyl compounds (eg, allyl esters such as allyl acetate). This polymerizable unsaturated monomer (D) can be used alone or in combination of two or more.

The (meth) acyl of the polymerizable unsaturated monomer (D)
For example, (meth) acrylate,
(Meth) acrylamides, (meth) acrylonitrile
And so on. (Meth) acrylates include, for example,
Alkyl (meth) acrylate [for example, methyl (meth)
TA) acrylate, ethyl (meth) acrylate, professional
Pill (meth) acrylate, isopropyl (meth) ac
Relate, butyl (meth) acrylate, isobutyl
(Meth) acrylate, t-butyl (meth) acrylate
G, hexyl (meth) acrylate, octyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate
And C such as lauryl (meth) acrylate_{1 -18}A
Alkyl (meth) acrylate), cycloalkyl
(Meth) acrylate [for example, cyclohexyl (meth
Acrylates, etc.), aryl (meth) acrylates
[For example, phenyl (meth) acrylate, etc.]
Aralkyl (meth) acrylate [for example, benzyl (meth)
Acrylates, etc.], hydroxyalkyl (meth)
Acrylates [for example, 2-hydroxyethyl, 2-h
Hydroxypropyl (such as (meth) acrylate
Kishi-C_2-4Alkyl (meth) acrylate, etc.],
Glycidyl (meth) acrylate, dialkylamino-
Alkyl (meth) acrylate [for example, 2- (dimethyl
Ruamino) ethyl (meth) acrylate, 2- (diethyl
Di-C such as ruamino) ethyl (meth) aclay _1-4
Alkylamino-C_2-4Alkyl (meth) aclay
And the like).

(Meth) acrylamides include, for example,
(Meth) acrylamide, hydroxyalkyl (meth)
Acrylamide, [for example, N-hydroxy-C _1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide, etc.], alkoxyalkyl (meth) acrylamide, [for example, N-hydroxymethyl (meth) acrylamide, etc. C _1-4 alkoxy-C _1-4 alkyl (meth) acrylamide], diacetoxy (meth) acrylamide and the like.

Preferred (meth) acrylic monomers include, for example, (meth) acrylates [eg, C
_{1 over 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, etc.], (meth)
Acrylamides and the like. Further, preferred (meth) acrylic monomers include C _2-10 alkyl acrylate, C _1-6 alkyl methacrylate,
Hydroxy-C _2-3 alkyl (meth) acrylate,
Glycidyl (meth) acrylate, di-C _1-3 alkylamino-C _2-3 alkyl (meth) acrylate and the like can be mentioned.

The aromatic vinyls include, for example, styrene,
α-methylstyrene, vinyltoluene and the like are included, and styrene is often used. Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl versatate (VeoVa), and the like. Halogen-containing vinyls include, for example, vinyl chloride, vinylidene chloride, and the like. Other polymerizable unsaturated monomers (D)
The above-mentioned polymerizable unsaturated monomer (A) having a hydrolyzable silyl group may be used.

As such a polymerizable unsaturated monomer (D), usually, a hard monomer [for example, a glass transition temperature of 80 to 120 of methyl (meth) acrylate, styrene or the like] is used.
° C. (in particular 90 to 105 ° C.) and the monomer component forming the homopolymer of the order, the soft monomer [e.g., a glass transition temperature -8 such as acrylic acid C _{2 -10} alkyl ester
Monomer component that forms a homopolymer at about 5 ° C. to 10 ° C. (particularly −85 ° C. to −20 ° C.)].

As described above, when a hard monomer and a soft monomer are usually used as the polymerizable unsaturated monomer (D), the compounding ratio thereof is not particularly limited, but for example, 10 to 90% by weight of the hard monomer (for example, 15-85% by weight, preferably 20-80% by weight, more preferably 25-75% by weight, especially 30-70% by weight, soft monomer 10-90% by weight (for example, 15-85% by weight,
Preferably 20 to 80% by weight, more preferably 25 to 80% by weight.
75% by weight, especially 30 to 70% by weight).

Further, in the acrylic resin (a) having a hydrolyzable silyl group, a monomer (C) having an alkylene oxide unit represented by the following general formula (1) is used as a copolymerization component of the resin. May be used. By using the monomer (C), the glossiness of the recording material of the present invention is improved.

Embedded image (Wherein, R ¹ represents a hydrogen atom, a methyl group or a hydroxyl group, R ² represents a hydrogen atom or a methyl group, and n represents 1 to 5
And m represents an integer of 1 to 20. )

Examples of the monomer (C) having a polyalkylene oxide unit include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and dipropylene glycol (meth). )
Acrylate, tripropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol
Examples include (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol polytetramethylene glycol (meth) acrylate, polypropylene glycol polytetramethylene glycol (meth) acrylate, and glycerol (meth) acrylate.

In the present invention, when the alkylene oxide unit-containing monomer (C) is not used, each of the above-mentioned copolymer components is a polymerizable unsaturated monomer containing a hydrolyzable silyl group having a long inter-silicon bridge (A). ) 0.5 to 50% by weight, an ion-forming group-containing polymerizable unsaturated monomer (B) 1 to 20% by weight,
Other polymerizable unsaturated monomer (D) ｛100-((A)
+ (B)｝% by weight for solution polymerization.

The polymerizable unsaturated monomer containing a long hydrolyzable silyl group between silicon bridges (A) is used in an amount of 0.5 to 50% by weight of the total polymerizable unsaturated monomer. ~ 20
It is preferable to use weight%. If the proportion of the monomer (A) is less than 0.5% by weight, there may be a problem that the water resistance and the strength of the coating film are deteriorated. on the other hand,
If it exceeds 50% by weight, there may be a problem that the polymerization stability of the acrylic resin (a) and the storage stability when emulsified are reduced.

The ionizable group-containing polymerizable unsaturated monomer (B) accounts for 1 to 20% by weight of the total polymerizable unsaturated monomer.
It is preferably used in an amount of 2 to 10% by weight. If the proportion of the monomer (B) is less than 1% by weight, agglomerates are formed during emulsification, while if it exceeds 20% by weight, the water resistance of the coating film deteriorates. The other polymerizable unsaturated monomer (D) accounts for the balance of the monomers (A) and (B).

In the present invention, when the monomer (C) containing an alkylene oxide unit is used, each of the above-mentioned copolymerization components is a polymerizable unsaturated monomer (A) containing a long hydrolyzable silyl group between silicon bridges. 0.5 to 50% by weight, ion-forming group-containing polymerizable unsaturated monomer (B) 1 to 20% by weight, polyalkylene oxide unit-containing monomer (C) 5 to 20
% By weight, other polymerizable unsaturated monomer (D) ｛100-
((A) + (B) + (C)) The solution polymerization is carried out by using a ratio of {wt%}.

In the above, the polyalkylene oxide unit-containing monomer (C) is used in an amount of 5 to 20% by weight of the total polymerizable unsaturated monomers. There may be a problem that the effect of improving the glossiness does not appear. On the other hand, if it exceeds 20% by weight, there is a problem that the ink absorbability is reduced due to swelling and the pores are closed, or a problem that the polymerization stability of the acrylic resin (a) is reduced. May occur.
The other polymerizable unsaturated monomer (D) accounts for the balance of the monomers (A), (B), and (C).

In one embodiment of the present invention, each of the above-mentioned copolymer components is solution-polymerized, and the resulting resin solution is emulsified by adding water to obtain an aqueous resin composition. That is, each of the above copolymer components is mixed and copolymerized in the presence of a suitable organic solvent, and the polymer is alkali (for example, an alkylamine such as triethylamine, a cyclic amine such as morpholine, a triamine) or the like. Dissolved or dispersed using an alkanolamine, pyridine, ammonia, etc.) or an acid [eg, an inorganic acid (eg, hydrochloric acid, sulfuric acid, etc.), an organic acid (eg, carboxylic acid such as acetic acid, propionic acid, sulfonic acid, etc.)] Let it. The polymerization operation may be a batch type or a continuous type.

Examples of the organic solvent used in the solution polymerization include alcohols (eg, ethanol, isopropanol, n-butanol, etc.), aromatic hydrocarbons (eg,
Benzene, toluene, xylene, etc.), aliphatic hydrocarbons (eg, pentane, hexane, heptane, etc.), alicyclic
Formula hydrocarbons (eg, cyclohexane, etc.), esters (eg, ethyl acetate, n-butyl acetate, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, diethyl ether, dioxane, tetrahydrofuran, etc.), etc. Can be used. These organic solvents may be used alone or in combination of two or more. As the organic solvent, an alcohol such as isopropanol, an aromatic hydrocarbon such as toluene, and a ketone such as methyl ethyl ketone are usually used.

The amount of the organic solvent to be used is not particularly limited. For example, the amount of the organic solvent relative to the total amount of the polymerizable unsaturated monomer is (0.1 / 1 to 5/1) by weight, preferably (0/1). .5
/ 1 to 2/1).

In the solution polymerization, the polymerization may be started by heating with irradiation of an electron beam or an ultraviolet ray, but the polymerization is often started by using a polymerization initiator. Examples of the polymerization initiator include, for example, 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 peroxides (for example, potassium persulfate, sodium persulfate,
Persulfates such as ammonium persulfate, hydrogen peroxide, etc.), organic peroxides [for example, benzoyl peroxide, di-
t-butyl peroxide, cumene hydroxy peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc.] and a redox catalyst [for example, sulfite or bisulfite (for example, alkali metal salt, ammonium salt, etc.), L-ascorbin] A catalyst system comprising a combination of a reducing agent such as an acid or erythorbic acid and an oxidizing agent such as a persulfate (eg, an alkali metal salt or an ammonium salt) or a peroxide]. The polymerization initiators can be used alone or in combination of two or more.

The amount of the polymerization initiator to be used is, for example, 0.001 to 20% by weight based on the total weight of the polymerizable unsaturated monomer,
Preferably 0.01 to 10% by weight (for example, 0.1 to 1%)
0% by weight).

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

When the polymer contains a cationic group such as an amino group, an imide group or another cation-forming group, the use of an acid enhances the hydrophilicity and easily dissolves or emulsifies the polymer. can do. Such acids include:
For example, 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, etc .; saturated aliphatic polycarboxylic acids such as oxalic acid, adipic acid, etc. Acids, 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].

When the polymer has an acidic group such as a carboxyl group, the use of a base can easily dissolve or emulsify the polymer. Such bases include, for example, organic bases (eg, alkylamines such as triethylamine, cyclic amines such as morpholine, alkanolamines such as triethanolamine, pyridine, etc.), and inorganic bases (eg, ammonia, alkali metal hydroxides) Such)
And so on. The amount of the base used can be selected, for example, from the range of about 0.3 / 1 to 1.5 / 1 (molar ratio) of the base / acid group based on the total amount of the acid groups.

Emulsification of the polymer obtained by solution polymerization is as follows:
It can be performed in the presence or absence of an organic solvent.
When the polymer is dissolved or emulsified and dispersed in the presence of an organic solvent, a water-soluble organic solvent (for example, an alcohol such as isopropanol) is often used as the organic solvent. When the polymer is emulsified in the presence of an organic solvent, the organic solvent may be removed after the emulsification by evaporation or the like, and the emulsion may contain an organic solvent. When the organic solvent is removed before emulsifying the polymer, a low-boiling organic solvent (for example, a ketone such as methyl ethyl ketone) is often used.

When the polymer obtained by the solution polymerization is emulsified in the presence of an organic solvent, an additive (eg, an emulsifier, a pH adjuster, an acid, etc.) is added to an organic solution containing the polymer, and then added to water. Can be added to emulsify. In this case, it is preferable that water is gradually added by dropping or the like. The temperature at the time of emulsification is preferably low, for example, 70 ° C. or lower (eg, 5 to 70 ° C.), preferably 50 ° C. or lower (eg,
10 to 50 ° C.). The removal of the organic solvent after emulsification by adding water is performed, for example, at a temperature of 80 ° C. or lower (for example, about 5 to 80 ° C.) at normal pressure or under reduced pressure (for example, about 0.0001 to 1 atm). Often done.

In the solution polymerization, a chain transfer agent such as alcohols such as catechol, thiols, and mercaptans (eg,
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 aqueous emulsion thus obtained is in a range that does not impair the dispersion stability, adhesion, etc., for example, 0.01 to 2 μm.
Preferably it is 0.01 to 0.5 μm, more preferably 0.1 to 0.5 μm.
01 to 0.3 μm, still more preferably 0.01 to
It can be selected from a range of about 0.1 μm.

The aqueous resin composition obtained by emulsifying the acrylic resin (a) of the present invention may be an aqueous solution or an aqueous emulsion (aqueous polymer emulsion). Such an aqueous resin composition is an aqueous resin composition formed without using a special cross-linking resin such as a cross-linked product of an acrylic silicone oligomer containing a hydrolyzable alkoxysilyl group. Is high. In addition, by using this water-based resin composition, it is possible to obtain a coating agent with less fear of air pollution, poisoning, fire and the like, and with good workability.

The acrylic resin (a) of the present invention includes:
If necessary, for example, stabilizers such as lubricants, antioxidants, light stabilizers, ultraviolet absorbers, heat stabilizers, radical scavengers, quenchers, antistatic agents, plasticizers, thickeners, quenchers Various known additives such as a foaming agent may be added.

Light stabilizers and ultraviolet absorbers such as hindered amine compounds, benzoate compounds, benzotriazoles, benzophenones and formamidines are effective for imparting and improving weather resistance.

(B) Inorganic fine particles The inorganic fine particles (b) used in the present invention include, for example,
Alumina, silica, calcium carbonate, aluminum hydroxide, calcium silicate and the like can be mentioned. Preferred is silica, and particularly preferred is colloidal silica. For the gloss and transparency of the ink receiving layer, those having a small particle size are preferred. For example, 1 to 500 nm, preferably 2 to 10 nm
0 nm, more preferably 3 to 30 nm. The shape of the inorganic fine particles may be any of a spherical shape, a flat shape, a column shape, and a bead shape.

The acrylic resin (a) thus obtained and the inorganic fine particles (b) are mixed to prepare a resin composition as a coating agent used for forming an ink receiving layer. Here, water or an aqueous solvent such as alcohol may be added to improve coating properties and drying properties. The mixing method is
A conventionally known method can be used. The mixing ratio is
The inorganic fine particles (b) are 50 to 2,000 parts by weight based on 100 parts by weight of the acrylic resin (a). Preferably, the inorganic fine particles (b) are 200 to 2,000 parts by weight based on 100 parts by weight of the acrylic resin (a). More preferably, the amount of the inorganic fine particles (b) is 300 to 1000 parts by weight based on 100 parts by weight of the acrylic resin (a). 100 parts by weight of the acrylic resin (a) and 2 parts of the inorganic fine particles (b)
If the amount exceeds 2,000 parts by weight, the film-forming property tends to decrease, and 5
If the amount is less than 0 parts by weight, the quick-drying property and the ink-absorbing property decrease.

The ink receiving layer may contain, if necessary, other components such as a polymer having no crosslinkable group or an aqueous emulsion containing the polymer (for example, an ethylene-vinyl acetate copolymer emulsion, acetic acid Vinyl emulsion, etc.).

The ink receiving layer may contain a powder (eg, a pigment). Here, as the powder, for example, inorganic powder (white carbon, fine-particle calcium silicate, zeolite, magnesium aminosilicate, calcined silica, fine-particle magnesium carbonate, fine-particle alumina,
Talc, kaolin, deramikaolin, clay, heavy calcium carbonate, light calcium carbonate, magnesium carbonate,
Titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium silicate, calcium sulfate, mineral powders such as sericite, bentonite, scumite, etc.), organic powders (polystyrene resin, urea resin, melamine resin) Or crosslinked or non-crosslinked organic fine particles such as benzoguanamine resin, and organic powders such as fine hollow particles. These powders are 1
Species or two or more species can be appropriately selected and used in combination.

In the case of using a granular material, a hydrophilic polymer such as a saponified vinyl acetate copolymer can be used as the binder resin. The ratio of the granular material to the binder resin is 0.1 to 80 parts by weight, preferably about 0.2 to 50 parts by weight, based on 100 parts by weight of the binder resin. In the ink receiving layer, conventional additives such as defoamers, coating improvers, thickeners, surfactants, lubricants, stabilizers (antioxidants, ultraviolet absorbers, Heat stabilizer), an antistatic agent, an anti-blocking agent, and the like.

(C) Substrate In the present invention, the substrate on which the ink receiving layer is formed may be opaque, translucent or transparent depending on the application.
A substrate used for an overhead projector (OHP) or the like is usually transparent. The material of the substrate is not particularly limited, and examples of the substrate that can be used include paper,
Coated papers, nonwovens, plastic films and synthetic papers are included.

Examples of the polymer constituting the plastic film and the synthetic paper include polyolefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and poly (meth) acrylic. Acid esters, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivatives such as cellulose acetate,
Polyester (polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate, etc.), polycarbonate, polyamide (polyamide 6, polyamide 6)
/ 6, polyamide 6/10, polyamide 6/12, etc.), polyesteramide, polyether, polyimide, polyimideamide, polyetherester, and the like. Is also good.

As the polymer constituting these films or synthetic papers, polyolefins (especially polypropylene), polyesters (especially polyethylene terephthalate, etc.), polyamides and the like are usually used, and particularly, such as mechanical strength, workability and cost. From the viewpoint, polyester (particularly, polyethylene terephthalate) is preferred. As the paper or coated paper, for example, high quality paper, art paper, RC paper and the like can be used.

The thickness of the substrate can be selected according to the application, and is usually from 5 to 500 μm, preferably from about 10 to 300 μm. The base material has a sizing agent, an antioxidant, an ultraviolet absorber, a heat stabilizer,
Conventional additives such as lubricants and pigments may be used.

Further, in order to improve the adhesiveness with the ink receiving layer, a surface treatment such as a corona discharge treatment or an undercoat treatment may be performed.

(D) Method for Producing Recording Material The recording material of the present invention can be produced by forming an ink receiving layer comprising the resin composition for ink jet recording of the present invention on at least one surface of the above substrate. Each ink receiving layer can be formed by applying a coating solution prepared using an appropriate solvent (water, a hydrophilic solvent which may be water-soluble, a hydrophobic solvent or a mixed solvent thereof) to a substrate. When the resin composition containing the crosslinkable group-containing cationic acrylic copolymer is in the form of an aqueous emulsion, it is used in the form of an aqueous coating solution. The coating solution is formed by a conventional casting or coating method, such as 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, or the like. Is cast or applied. The ink receiving layer can be formed by applying a coating liquid containing the above components to at least one surface of the base material and drying. Further, if necessary, after the coating liquid is applied, a crosslinked ink absorbing layer may be formed by heating at an appropriate temperature selected from the range of about 50 to 150 ° C. In addition, a porous layer, an anti-blocking layer, a lubricating layer, an antistatic layer, and the like may be formed on the ink receiving layer, if necessary. Further, if necessary, the surface of the ink receiving layer may be subjected to a smoothing treatment such as a super calender.

The thickness of the ink receiving layer formed of the recording resin composition comprising the acrylic resin (a) having a hydrolyzable silyl group and the inorganic fine particles (b) can be selected according to the intended use. ５０50 μm, preferably 6-3
It is about 0 μm, usually about 5 to 30 μm.

[0078]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The methods for evaluating various characteristics of the recording sheets obtained in the examples and comparative examples are as follows. Using an inkjet printer (PM-770C manufactured by Seiko Epson Corporation), a color pattern using each color of cyan, yellow, magenta, and black was printed on the recording sheets obtained in Examples and Comparative Examples in a photo glossy paper mode. Then, an evaluation image was formed.

(Coating film strength) Using a pencil scratching tester, applying a load (50 g) to the coated ink receiving layer, performing a scratching test with pencils of various hardnesses, and visually determining the degree of tearing of the coating film. did. ：: No powder falling was observed when scratched with a pencil having a hardness of H or more. ：: No powder drop was observed when scratched with a HB pencil. Δ: Slight powder loss was observed when scratched with a HB pencil. ×: Powder falling easily observed when scratched with a pencil having a hardness of B or less.

(Ink Drying Property) After printing solid images of cyan, magenta, yellow, black and a mixed color of red, green, and blue using the above printer, 30 seconds later, PPC paper is placed on the printing portion. After applying a load (500 g / cm ² ) for 10 seconds, the PPC paper was peeled off, and the degree of transfer of the ink to the copy paper was visually determined based on the following criteria. ：: No transfer of ink to copy paper was observed at all. Δ: Slight transfer of ink was observed. ×: Marked transfer of ink.

(Print Image Quality)
A standard image was printed and visually judged according to the following criteria. ：: No poor image quality such as bleeding or unevenness is observed. Δ: Slightly poor image quality such as bleeding or unevenness is observed. X: Image quality defects such as bleeding and unevenness are remarkable, and a clear image cannot be obtained.

(Glossiness) The 60 ° glossiness of the recording sheet was calculated as follows.
It was measured using a gloss meter.

[Synthesis of Polymerizable Unsaturated Monomer (A ₁ ) Having Long Hydrolyzable Silyl Group Between Silicon Bridges]
551.5 parts by weight of methyl isobutyl ketone (hereinafter abbreviated as "MIBK") was placed in a 2 l reaction vessel equipped with a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer. (Addition polymer of ε-caprolactone to OH group of hydroxyethyl methacrylate) 362 parts by weight, γ-isocyanatopropyltriethoxysilane (manufactured by Nippon Unicar Co., Ltd., A-131)
0) 166 parts by weight, dibutyltin dilaurate 0.02
5 g was charged and reacted at 80 ° C. for 8 hours with stirring. The obtained macromonomer (A ₁ ) (solid content concentration 50
%) By GPC (gel permeation chromatography) method was 700.

[Synthesis of Polymerizable Unsaturated Monomer (A ₂ ) Having Long Hydrolyzable Silyl Group Between Silicon Bridges]
In a 2 liter reaction vessel equipped with a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer, 497 parts by weight of MIBK, polyethylene glycol monomethacrylate (manufactured by NOF Corporation)
362 parts by weight, Prenmer PE-200), 171 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Nippon Unicar Co., Ltd., A-1310), and 0.025 g of dibutyltin dilaurate.
Reaction was carried out at 8 ° C. for 8 hours. The resulting macromonomer (A
₂ ) The number average molecular weight by GPC of (solids concentration 50%) was 600.

[Synthesis of Acrylic Copolymer (a ₁ ) Having Hydrolyzable Silyl Group] In a 2 l reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, isopropyl alcohol (hereinafter referred to as “a”) 175 parts by weight of azobisisobutyronitrile (hereinafter abbreviated as “AIBN”) 0.62 are added thereto while stirring.
The mixture was added and dissolved by weight and heated to 80 ° C. As copolymerization components, 96 parts by weight of methyl methacrylate (hereinafter abbreviated as “MMA”) and n-butyl acrylate (hereinafter “B”)
A ". ) 62 parts by weight of macromonomer (A ₁ )
30 parts by weight (solid content concentration: 50%) and 6 parts by weight of acrylic acid (hereinafter abbreviated as "AA") were mixed, and added dropwise to the reaction vessel over about 4 hours using a dropping funnel. After dropping,
As an additional catalyst, 0.25 parts by weight of AIBN was dissolved in 25 parts by weight of IPA, added dropwise to the reaction vessel, and the reaction was maintained for another 2 hours. After completion of the polymerization, while stirring, 7.2 parts by weight of 25% ammonia water was added to the reaction vessel, and 705 parts by weight of water was dropped into the reaction vessel over about 2 hours to emulsify. After emulsification, the IPA was evaporated using a rotary evaporator to obtain the desired hydrolyzable silyl group-containing acrylic resin (a ₁ ). The solid content of this resin composition was 40% by weight.

[Synthesis of Hydrolyzable Silyl Group-Containing Acrylic Copolymer (a ₂ )] Instead of the macromonomer (A ₁ ) as a copolymer component, 3-methacryloxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd.) , A-174), except that a polymerization reaction and emulsification were carried out in the same manner as described above to obtain a hydrolyzable silyl group-containing acrylic resin (a ₂ ). The solid content of this resin composition was 40% by weight.

[Synthesis of Hydrolyzable Silyl Group-Containing Acrylic Copolymer (a ₃ )] The polymerization reaction and emulsification are carried out in the same manner as described above except that the macromonomer (A ₁ ) is not used. A group-containing acrylic resin (a ₃ ) was obtained. The solid content of this resin composition is 40% by weight.
Met.

[Synthesis of Acrylic Copolymer (a ₄ ) Having Hydrolyzable Silyl Group] 175 parts by weight of IPA was placed in a 2 l reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer. AIBN with stirring
0.62 parts by weight was added and dissolved, and the mixture was heated to 80 ° C. 96 parts by weight of MMA, 62 parts by weight of BA,
30 parts by weight of the macromonomer (A ₂ ) (solid content concentration: 50%) and 6 parts by weight of AA were mixed and dropped into the reaction vessel over about 4 hours using a dropping funnel. After completion of the dropwise addition, 0.25 parts by weight of AIBN as an additional catalyst was dissolved in 25 parts by weight of IPA, added dropwise to the reaction vessel, and the reaction was maintained for another 2 hours. After completion of the polymerization, while stirring, 7.2 parts by weight of 25% ammonia water was added to the reaction vessel, and 705 parts by weight of water was dropped into the reaction vessel over about 2 hours to emulsify.
After emulsification, IPA was evaporated using a rotary evaporator to obtain a hydrolyzable silyl group-containing acrylic resin (a ₄ ). The solid content of this resin composition was 40% by weight.

[Synthesis of Acrylic Copolymer (a ₅ ) Having Hydrolyzable Silyl Group] 175 parts by weight of IPA was placed in a 2 liter reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer. AIBN with stirring
0.62 parts by weight was added and dissolved, and the mixture was heated to 80 ° C. 96 parts by weight of MMA, 62 parts by weight of BA,
30 parts by weight of macromonomer (A ₁ ) (solid content concentration: 50%), 22 parts by weight of polyethylene glycol monomethacrylate (manufactured by NOF Corporation, Plenmer PE-200),
6 parts by weight of AA were mixed and dropped into the reaction vessel over about 4 hours using a dropping funnel. After completion of the dropwise addition, 0.25 parts by weight of AIBN as an additional catalyst was dissolved in 25 parts by weight of IPA, added dropwise to the reaction vessel, and the reaction was maintained for another 2 hours.
After the polymerization, 7.2 parts by weight of 25% aqueous ammonia was added to the reaction vessel while stirring was continued, and 705 parts by weight of water was added to about 2 parts by weight.
The mixture was dropped into the reaction vessel over time to emulsify. After emulsification, use a rotary evaporator to
PA was evaporated to obtain a hydrolyzable silyl group-containing acrylic resin (a ₅ ). The solid content of this resin composition is 30% by weight.
Met.

[Synthesis of Hydrolyzable Silyl Group-Containing Acrylic Copolymer (a ₆ )] A polymerization reaction and emulsification were carried out in the same manner as in the synthesis of (a ₅ ) except that the macromonomer (A ₁ ) was not used. Was carried out to obtain a hydrolyzable silyl group-containing acrylic resin (a ₆ ). The solid content of this resin composition was 30% by weight.

[Synthesis of Hydrolyzable Silyl Group-Containing Acrylic Copolymer (a ₇ )] Polyethylene glycol monomethacrylate (Plenmer PE-20 manufactured by NOF Corporation)
Except that the amount of 0) and 83 parts by weight, the _(a 5)
The polymerization reaction and the emulsification were carried out in the same manner as in the synthesis of, but the viscosity increased during the polymerization, and a hydrolyzable silyl group-containing acrylic resin was not obtained.

Example 1 On art paper (NK white tong loss 180.0) having a thickness of 190 μm, based on 100 parts by weight of a hydrolyzable silyl group-containing acrylic resin (a ₁ ), beaded colloidal silica (Nissan) The recording sheet 1 was obtained by applying a coating solution containing 900 parts by weight of Snowtex PS-M (manufactured by Chemical Co., Ltd.) so as to have a dry thickness of 45 μm.

Example 2 A beaded colloidal silica (Nissan Chemical Co., Ltd.) was used on the base material used in Example 1 based on 100 parts by weight of a hydrolyzable silyl group-containing acrylic resin (a ₂ ).
Co., Ltd., 400 parts of Snowtex PS-M) was applied to a thickness of 45 μm when dried to obtain a recording sheet 2.

[Example 3] A beaded colloidal silica (Nissan Chemical Co., Ltd.) was used on the base material used in Example 1 based on 100 parts by weight of a hydrolyzable silyl group-containing acrylic resin (a ₄ ).
The recording sheet 3 was obtained by applying a coating solution containing 900 parts of Snowtex PS-M) to a dry thickness of 45 μm.

Example 4 Hydrolyzability used in Example 1
Silyl group-containing acrylic resin (a₁) Instead of (a ₂)
Except that the recording sheet 4 was used in the same manner as in Example 1.
I got

Comparative Example 1 Hydrolyzability used in Example 2
Silyl group-containing acrylic resin (a₂) Instead of (a ₃)
Except that the recording sheet 5 was used in the same manner as in Example 2.
I got

[Comparative Example 2] A beaded colloidal silica (Nissan Chemical Co., Ltd.) was used on the substrate used in Example 1 with respect to 100 parts by weight of a hydrolyzable silyl group-containing acrylic resin (a ₂ ).
The recording sheet 6 was obtained by applying a coating solution containing 25 parts by weight of Snowtex PS-M) to a dry thickness of 45 μm. Table 1 shows the evaluation results of the recording sheets obtained in the above Examples and Comparative Examples.

[0099]

[Table 1]

Example 5 On art paper (NK white tong loss 180.0) having a thickness of 190 μm, based on 100 parts by weight of a hydrolyzable silyl group-containing acrylic resin (a ₅ ), beaded colloidal silica (Nissan) The recording sheet 7 was obtained by applying a coating solution containing 400 parts by weight of Snowtex PS-M (manufactured by Chemical Co., Ltd.) to a thickness of 45 μm when dried.

Comparative Example 3 Hydrolyzability used in Example 4
Silyl group-containing acrylic resin (a₅) Instead of (a ₆)
Except that the recording sheet 8 was used in the same manner as in Example 4.
I got

Comparative Example 4 Hydrolyzability used in Example 4
Silyl group-containing acrylic resin (a₅) Instead of (a ₃)
Except that the recording sheet 9 was used in the same manner as in Example 4.
I got

[Reference Example] The hydrolyzable resin used in Example 4 was used.
Ryl group-containing acrylic resin (a₅) Instead of (a ₇)
The recording sheet was obtained in the same manner as in Example 4.
Increases the viscosity during the synthesis of the copolymer to obtain a recording sheet
Could not. Obtained in the above Examples and Comparative Examples
Table 2 shows the evaluation results of the recording sheets.

[0104]

[Table 2]

[0105]

According to the present invention, by using a resin composition in which a hydrolyzable silyl group-containing acrylic resin and inorganic fine particles (silica) are blended in a specific ratio in an ink receiving layer of an ink jet recording material, the coating film strength and ink absorption can be improved. In particular, the use of a hydrolyzable silyl group-containing acrylate resin having a long inter-silicon cross-linking property has an appropriate elasticity, so that the effect is further improved. Furthermore, when a monomer having a polyalkylene oxide unit is copolymerized, using a hydrolyzable silyl group-containing acrylic resin,
Glossiness is improved in addition to the above.

Claims (10)

[Claims] 1. An inorganic fine particle (b) 50 based on 100 parts by weight of an acrylic resin (a) having a hydrolyzable silyl group.
A resin composition for ink jet recording, comprising ２０００2000 parts by weight. 2. An acrylic resin (a) having a hydrolyzable silyl group, wherein the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon crosslinks is 0.5 to 50% by weight.
And 1 to 20% by weight of a polymerizable unsaturated monomer (B) having at least one ion-forming group and another polymerizable unsaturated monomer (D) Ｄ100-((A) + (B ))｝
2. A copolymer obtained by copolymerizing the polymer with a weight%.
4. The resin composition for inkjet recording according to item 1. 3. An acrylic resin (a) having a hydrolyzable silyl group, wherein the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon bridges is 0.5 to 50% by weight.
And 1 to 20% by weight of a polymerizable unsaturated monomer (B) having at least one ion-forming group, and a monomer (C) containing an alkylene oxide unit represented by the following general formula (1). ) 5-20% by weight and other polymerizable unsaturated monomers (D) @ 100-((A) + (B) +
The resin composition for ink jet recording according to claim 1, which is a copolymer obtained by copolymerizing (C))｝% by weight. Embedded image (Wherein, R ¹ represents a hydrogen atom, a methyl group or a hydroxyl group, R ² represents a hydrogen atom or a methyl group, and n represents 1 to 5
And m represents an integer of 1 to 20. ) 4. An aqueous resin composition obtained by adding water to a resin solution obtained by solution polymerization to emulsify an acrylic resin (a) having a hydrolyzable silyl group and then removing a polymerization solvent. The ink-jet recording resin composition according to claim 1, which is a product. 5. The ink-jet recording method according to claim 2, wherein the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between the silicon bridges is represented by the following general formula (2). Resin composition. Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ ,
R ⁵ represents an alkyl group, an aryl group, an aralkyl group, an alkoxyl group, an aryloxy group, a hydroxyl group or an alkylthio group which may be the same or different; X represents a halogen atom; r is an integer of 1 to 20; 0-2
Indicates an integer. ) 6. The ink-jet recording apparatus according to claim 2, wherein the polymerizable unsaturated monomer (A) having a long hydrolyzable silyl group between silicon crosslinks is represented by the following general formula (3). Resin composition. Embedded image (Wherein, R ⁶ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and R ⁹ is a hydrogen or 1 to 10 carbon atoms.
10 alkyl groups, aryl groups or aralkyl groups, X
Is a hydrolyzable group selected from the group consisting of halogen, alkoxy, acyloxy, ketoximate, amino, acid amide, aminooxy, mercapto and alkenyloxy groups, o + p is 2 or more, and o and p are 0 to 100.
And q represents an integer of 0 to 2. ) 7. The resin composition for ink jet recording according to claim 1, wherein the acrylic resin (a) having a hydrolyzable silyl group is an aqueous resin composition having an average particle diameter of 0.01 to 0.1 μm. 8. An inorganic fine particle (b) having an average particle size of 1 to 5
The resin composition for inkjet recording according to claim 1, which has a thickness of 00 nm. 9. The resin composition for ink jet recording according to claim 1, wherein the inorganic fine particles (b) are colloidal silica. 10. An ink jet recording material comprising at least one void phase formed from the resin composition according to claim 1 on a substrate as an ink receiving layer.