JP2000290322A - Silane coupling agent and ink jet recording medium using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel silane coupling agent capable of improving the light fastness without lowering the recording density, color developability and water fastness of an ink jet recording medium mainly composed of an inorganic pigment, and the silane. Provided is an ink jet recording medium having improved light fastness by a coupling agent. SOLUTION: The polymer type silane coupling agent represented by the following general formula (1). -(X) a- (Y) b- (Z) c- General formula (1) In the above formula (1), X is a copolymerizable monomer having a group capable of producing a silanol group by hydrolysis. Y represents a repeating unit formed by polymerization of a copolymerizable monomer having a group having an ultraviolet absorbing function or a group having a light stabilizing function, and Z represents X, It represents a repeating unit formed by polymerization of a copolymerizable monomer having an ethylenically unsaturated group other than Y. a + b + c = 100
A is 10 to 90 mol% and b is 10 to 90 mol%
Mol% and c are 0 to 80 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silane coupling agent capable of improving water resistance and light resistance without deteriorating the recording density and color developability of an ink jet recording medium containing an inorganic pigment as a main component. The present invention relates to an ink jet recording medium using an agent.

[0002]

2. Description of the Related Art An ink jet recording system is a system in which ink droplets ejected from a nozzle at a high speed are adhered to a recording material for recording, and has features such as easy full-color printing and low printing noise. . In this method, conditions such as not causing clogging of the ink jet nozzle and having a vivid color tone are required. Currently, it is not possible to select.
There are commercially available high-quality papers devised to be rich in ink absorbency, coated papers coated with a porous pigment on the surface thereof, and coated films coated with a resin having ink absorbency as ink jet recording media. . When these ink jet recording materials are recorded and stored for a long period of time, the recorded image undergoes severe discoloration and discoloration. Therefore, there is a strong demand for an ink jet recording material having excellent light resistance.

There have been many reports for the purpose of improving the light fastness of recorded images. For example, in JP-A-57-87988 and JP-A-57-87989, an ultraviolet absorbent or an antioxidant is added to an ink jet recording medium to improve light resistance. When used, the image quality is impaired, the white paper portion is yellowed over time, and the effect of improving light resistance is insufficient. On the other hand,
In JP-A-3-166586, the recording material is Na, K, Ca,
The surface of silica is treated with a metal soap, hydroxide, salt or oxide of a metal selected from Mg, Al, Zn, Ba, Sr and Sn to improve the light fastness of the recording medium. Each of the above methods has a small effect, and it is hard to say that the light resistance has been improved.

Japanese Patent Application Laid-Open No. Hei 8-187935 discloses a method of generating an image having less fading by combining a recording medium containing a vanadyl salt and an ink containing a triarylmethane dye. The light resistance improving effect can be obtained only by the combination of the recording medium and the specific ink, so that the versatility is poor. Further, JP-A-8-17
In JP-A-4988, JP-A-10-29369, JP-A-10-2779859, etc., a monomer bonded with a quaternary ammonium salt is bonded to a group capable of quenching singlet oxygen or a group capable of absorbing ultraviolet light. An ink-jet recording material containing a copolymer of the above-described monomer in an ink receiving layer is disclosed, but has a drawback that the copolymer is poor in water resistance because it is water-soluble.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a novel silane coupling agent which can improve the light fastness without lowering the recording density, color developability and water fastness of an ink jet recording medium mainly composed of an inorganic pigment. It is another object of the present invention to provide an ink jet recording medium in which light resistance is improved by the silane coupling agent.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the ink jet recording layer has
It has been found that light resistance is greatly improved by including an inorganic pigment coated with a specific compound, and the present invention has been completed. A first aspect of the present invention is a polymer-type silane coupling agent represented by the following general formula (1). -(X) a- (Y) b- (Z) c- General formula (1) In the above formula (1), X is a copolymerizable monomer having a group capable of forming a silanol group by hydrolysis. Represents a repeating unit produced by polymerization, Y represents a repeating unit produced by polymerization of a copolymerizable monomer having a group having an ultraviolet absorbing function or a group having a light stabilizing function, and Z represents at least X, It represents a repeating unit formed by polymerization of a copolymerizable monomer having an ethylenically unsaturated group other than Y. a + b + c
= 100 mol%, a is 10 to 90 mol%, b is 1
0 to 90 mol% and c is 0 to 80 mol%.

A second aspect of the present invention is the polymer type silane coupling agent according to the first aspect of the present invention, wherein in the general formula (1), X is a repeating unit represented by the following general formula. It is.

Embedded image

Embedded image However, in the above general formulas (2) and (3),
R ₁ , R ₂ and R ₃ are an alkyl group or an alkoxy group, and at least one of R ₁ , R ₂ and R ₃ is an alkoxy group. R ₄ is a methyl group or a hydrogen atom, and A is an oxygen atom or NH. J is a divalent linking group, and m
Is 0 or 1.

[0008] A third aspect of the present invention is the first aspect of the present invention, wherein in the general formula (1), Y is a repeating unit represented by the following general formulas (4) and (5). The silane coupling agent is a polymer type silane coupling agent.

Embedded image

Embedded image However, in the above general formulas (4) and (5),
R ₄ , A, J and m have the same meanings as in formula (2). R ₅
Are hindered amine compounds, benzophenone compounds, benzotriazole compounds, salicyl compounds,
Or a residue obtained by removing a hydrogen atom from a phenolic compound.

A fourth aspect of the present invention is the first aspect of the present invention, wherein Z in the general formula (1) has a cationic group represented by the following general formulas (6) to (8). It is a polymer type silane coupling agent.

Embedded image

Embedded image

Embedded image However, in the above general formula (6), R ₄ , A, J and m
Has the same meaning as in the general formula (2), and in the general formulas (6) to (8), X ⁻ represents an anion.

A fifth aspect of the present invention is an ink jet recording material comprising the polymer silane coupling agent according to the first to fourth aspects of the present invention.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polymer type silane coupling agent of the present invention includes a monomer (X) having a group capable of generating a silanol group by hydrolysis, a structural unit having a group having an ultraviolet absorbing function or a group having a light stabilizing function, that is, It is a copolymer of a monomer (Y) having a residue obtained by removing a hydrogen atom from a hindered amine compound, a benzophenone compound, a benzotriazole compound, or a phenol compound, and another monomer (Z).

The monomer (X) having a group capable of forming a silanol group by hydrolysis includes vinyl silanes, acryl silanes and methacryl silanes. Examples thereof include the following. Hereinafter, in the present specification, the expression “(meth) acryl” is used to collectively refer to acrylic and methacryl.

(1) Vinylsilanes: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β
-Methoxyethoxy) silane, vinyltriacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinylmethyldimethoxysilane, vinyldimethoxyethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltriiso Propoxysilane, vinyltri-n-butoxysilane, vinyltri-s
ec-butoxysilane, vinyltrihexyloxysilane, vinyldimethoxyoctyloxysilane, vinylmethoxydihexyloxysilane, vinyltrioctyloxysilane, vinylmethoxydilauryloxysilane,
Vinyldimethoxylauryloxysilane, vinylmethoxydioleyloxysilane and vinyldimethoxyoleyloxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane,
-Styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, trimethoxysilylpropylallylamine.

(2) (meth) acrylsilanes: γ-
(Meth) acryloxypropyltrimethoxysilane,
γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltris (β-methoxy Ethoxy) silane, γ- (meth) acryloxypropyltriacetoxysilane,
(Meth) acryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride.

The monomer (Y) having a residue obtained by removing a hydrogen atom from a structural unit having a group having an ultraviolet absorbing function or a group having a light stabilizing function is a hindered amine-based structural unit,
Examples thereof include a benzophenone-based structural unit, a benzotriazole-based structural unit, a salicylic acid-based structural unit, and a phenol-based structural unit, and examples thereof include the following.

(1) Hindered amine compounds: piperidine, 2-methylpiperidine, 2-ethylpiperidine, 3,5-dimethylpiperidine, 4-piperidinopiperidine, 4-pyrrolidinopiperidine, 2,2,6,6 −
Tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, ethylpipecolinate, phenyl-
4-piperidinyl carbonate, bis (2,2,6,6
-Tetramethylpiperidinyl) -4-sebacate, bis (N-methyl-2,2,6,6-tetramethylpiperidinyl) -4-sebacate, tetrakis (2,2,6,6
-Tetramethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperidine and hindered amines thereof A salt of a system compound and an acid, which has the effect of increasing the hydrophilicity or water solubility of the polymer silane coupling agent of the present invention.

(2) Benzophenone compounds: 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4
-Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (2-methoxy-4 -Hydroxy-5-benzoylphenyl) methane, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 4-hydroxy-4- (2
-(Meth) acryloyloxy) ethoxybenzophenone.

(3) Benzotriazole compounds: 2
-(2'-hydroxy-5'methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-3 ', 5' -Di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methylphenyl-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2-
[2'-hydroxy-3 '-(3 ", 4", 5 ", 6"
-Tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6
(2H-benzotriazol-2-yl) phenol], 2- [2′-hydroxy-5 ′-(methacryloyloxy) phenyl] benzotriazole, 2- [2 ′
-Hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-
3'-t-butyl-5 '-(methacryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-3'-methyl-5'-(acryloyloxy) phenyl] benzotriazole, 2- [2'- Hydroxy-
5 '-(methacryloyloxypropyl) phenyl]-
5-chlorobenzotritriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-
5 '-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-
3'-methyl-5 '-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl]
-5-chlorobenzotriazole, 2- [2'-hydroxy-5 '-(acroyloxybutyl) phenyl]-
5-methylbenzotriazole, [2-hydroxy-3
-T-butyl-5- (acryloyloxyethoxycarbonylethyl) phenyl] benzotriazole.

(4) Salicylic acid compounds: phenyl salicylate, pt-butylphenyl salicylate, 5
-Sulfosalicylate, p-octylphenyl salicylate.

(5) Phenolic compounds: 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- ( 3,5-di-t-butyl-4
-Hydroxyphenyl) propionate, bisphenol type: 2,2'-methylenebis (4-methyl-6-t-
Butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), 4,
4′-butylidenebis (3-methyl-6-t-butylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane, 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, tetrakis- (methylene-3- (3'5'-di-t-butyl-
4'-hydroxyphenyl) propionate) methane,
Bis (3,3′-bis- (4′-hydroxy-3′-t
-Butylphenyl) butyric acid) glycol ester, 1,3,5-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -S-triazine-
2,4,6- (1H, 3H, 5H) trione, tocophenol (s).

Among the monomers constituting the polymer type silane coupling agent, the monomers (Z) other than the above X and Y are:
Examples of the nonionic monomer, anionic monomer, and cationic monomer include, for example, the following.

(1) Nonionic monomers: olefins such as ethylene, propylene, and styrene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate and allyl acetate; and halogens such as vinyl chloride and vinyl bromide. Unsaturated carboxylic esters such as vinyl chloride, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene Glycol esters such as glycol (meth) acrylate and polyethylene glycol (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, N-isopropyl (meth) acrylamide, N, N
-Dimethylaminoethyl (meth) acrylate, N, N
-(Meth) acrylic compounds such as dimethylaminopropyl (meth) acrylamide, acryloylmorpholine, N-vinylpyrrolidine, N-vinylimidazole,
Nitrogen-containing vinyl compounds such as N-vinylpyrrolidone.

(2) Anionic monomers: unsaturated compounds such as (meth) acrylic acid, (anhydride) maleic acid, fumaric acid, crotonic acid, itaconic acid and ethylenesulfonic acid, or salts thereof.

(3) Cationic monomers: N, N, N-trimethylallylamine, N, N-dimethyldiallylamine, N-methyltriallylamine, N, N, N-trimethylammoniumethyl (meth) acrylate hydrochloride,
N, N, N-trimethylammoniumpropyl acrylate hydrochloride, vinyloxyethyltrimethylammonium hydrochloride, diallyldimethylammonium chloride,
Trimethyl-m or p-vinylbenzylammonium sulfonate, trimethyl-m or p-vinylbenzylammonium acetate, N-methyl-o, m, or p-aminostyrene hydrochloride, 2,3-dimethyl-1-
Vinyl imidazolium hydrochloride, N-methyl vinyl succinimide and the like. Further, the above quaternary ammonium salts.

The above quaternary ammonium salts can be synthesized by causing the corresponding amine to act as an alkylating agent. Examples of the alkylating agent include dimethyl sulfate, diethyl sulfate, benzyl chloride, methyl chloride, and monochloroacetic acid. The quaternary salification by an alkylating agent may be carried out by subjecting a monomer having a corresponding primary to tertiary amine to alkylation in advance to obtain a quaternary amine monomer and then subjecting it to copolymerization. Alkylation may be performed after copolymerization using a monomer having a graded amine.

As described above, a monomer (X) having a group capable of forming a silanol group by hydrolysis, a monomer (Y) having a group having an ultraviolet absorbing ability or a light stabilizing function,
And the other monomer (Z) may be used in an appropriate combination. In that case, each monomer may be used alone,
Several types may be used in combination.

The copolymerization ratio of the copolymer of X, Y and Z constituting the polymer type silane coupling agent [(X) a:
(Y) b: (Z) c] can be set as appropriate. The silane coupling agent used in the ink jet recording medium of the present invention is such that a + b + c = 100 mol%,
90 mol%, b is in the range of 10 to 90 mol%, and c is in the range of 0 to 80 mol%. The copolymerization is random copolymerization,
Any of block copolymerization may be used, and the arrangement of X, Y, and Z is arbitrary.

When Z is a hydrophilic monomer, when the ratio of Z is high, a water-soluble polymer type silane coupling agent can be obtained. Through the self-dispersing type, the properties can be largely controlled to the water-insoluble type. When the silane coupling agent of the present invention is used for the production of an ink jet recording medium, it is convenient for the production of the ink jet recording medium to be water-soluble. Preferably, the monomer (Z)
Is more preferable, since the dye in the ink can be fixed.

The content of the polymer type silane coupling agent with respect to the pigment is not particularly limited as long as it is effective, but it is in the range of 0.1 to 100 parts, preferably 1 to 50 parts per 100 parts of the pigment. is there. X and Y are essential components for improving the water fastness and light fastness of the image. However, if the content is too large relative to the pigment, it is uneconomical and impairs the ink absorbency of the recording layer. .

The polymer type silane coupling agent of the present invention can be obtained by copolymerizing a mixture of the above monomers X, Y and Z in a solvent. Use of water as a reaction solvent is not preferred because the silanol group of X is easily hydrolyzed. When a water-insoluble monomer is used, it is preferable to use an alcohol solvent. Furthermore, anionic polymerization or radical polymerization can be used for the copolymerization reaction, but 4,4′-azobis (isobutyronitrile), 2,2′-azobis (2-amidinopropane) hydrochloride, etc. are used. General radical polymerization is preferred. The polymerization initiator is used in the range of 0.01 to 3% by weight based on the mixture of the monomers. The polymerization temperature is -90 for anionic polymerization.
-30 ° C, 30-100 in case of radical polymerization
It is in the range of ° C.

The polymerization method is not particularly limited, and any known method may be used. After the polymerization, post-treatments such as neutralization and drying may be performed as necessary.

The ink-jet recording medium of the present invention comprises:
A recording layer mainly composed of a pigment and a binder is provided on a support, and the recording layer may have a multilayer structure. The effect of the pigment contained in the recording layer is that, since it has a large specific surface area, the ink absorption speed is high, good image quality is obtained, and the ink drying time is short.

The support is not particularly limited, and may be transparent or opaque. For example, cellophane, polyethylene, polypropylene, soft polyvinyl chloride, hard polyvinyl chloride, plastic films such as polyester, high quality paper, art paper, coated paper, cast coated paper,
Paper such as foil paper, kraft paper, polyethylene laminated paper, impregnated paper, vapor-deposited paper, and water-soluble paper, metal foil, synthetic paper, cloth, and the like are appropriately used.

As the pigment, commercially available pigments such as silica,
Alumina silicate, kaolin, clay, calcined clay,
Zinc oxide, tin oxide, aluminum oxide, aluminum hydroxide, boehmite, pseudo-boehmite, calcium carbonate, satin white, aluminum silicate, smectite, magnesium silicate, magnesium carbonate, magnesium oxide,
Various pigments known in the general coated paper field, such as diatomaceous earth, styrene-based plastic pigment, urea resin-based plastic pigment, and benzoguanamine-based plastic pigment, can be appropriately used. Among these pigments, silica, boehmite and pseudo-boehmite are particularly preferable because they have a large pore volume and can absorb a large amount of ink.

In order to produce an ink jet recording medium having a high recording density, ultrafine particles having an average particle diameter of 1 μm or less are preferably used. More preferably, the average particle size is 3 to
Average particle size of 10 to 30 formed by aggregation of primary particles of 40 nm
Use secondary particles of 0 nm. If the primary particle size of the ultrafine secondary particles is too small, the ink absorbency is poor. On the other hand, if the primary particle size is too large, the transparency of the recording layer is reduced, and it is difficult to obtain a high recording density. If the secondary particle size is too small, the film formability of the coating film is poor, and the coating film may have many cracks. On the other hand, if the secondary particle size is too large, the ink penetrates to the lower part of the recording layer, and lowers the recording density.

The method for producing ultra-fine particles of 1 μ or less is not particularly limited, but it can be obtained by applying a strong force to a commercially available pigment (several microns) by mechanical means. That is, it can be obtained by a breaking down method (a method of subdividing a bulk raw material). As mechanical means,
Examples include mechanical methods such as an ultrasonic homogenizer, a pressure homogenizer, a nanomizer, a high-speed rotation mill, a roller mill, a container driving medium mill, a medium stirring mill, a jet mill, and a sand grinder. The obtained ultrafine particles may be in the form of a colloid or a slurry. In the present invention, all the average particle diameters are measured by an electron microscope (SEM and TE).
M) is the particle size (Martin size) observed (see “Particle Handbook”, Asakura Shoten, p. 52).

In the ink jet recording medium of the present invention, a method in which a polymer silane coupling agent obtained by copolymerization is directly blended with a coating material and coated, and then heated to react with a pigment, After applying the agent solution on the coating layer, a method of reacting with the pigment by heating, a polymer type silane coupling agent is added to the pigment slurry in advance, and after heating and reacting, various additives are added. To make it contained in the coating layer.

In the case of a recording layer containing a pigment as a main component, it is necessary to add an adhesive (binder) for the pigment. Examples of the adhesive include water-soluble resins such as polyvinyl alcohol (hereinafter referred to as PVA), casein, soybean protein, starch, cellulose derivatives such as carboxymethylcellulose and methylcellulose, styrene-butadiene copolymer, methylmethacrylate-butadiene copolymer and the like. Known adhesives (binders) generally used for coated paper such as conjugated diene polymer latex, acrylic polymer latex, and vinyl copolymer latex such as styrene-vinyl acetate copolymer are used alone or in combination. Used as In order to increase the adhesiveness between the recording layer and the support or between the recording layers, a water-soluble resin, particularly PVA, is preferably used.

The weight ratio of the solid content of the pigment to the adhesive (binder) is 100/2 to 100/200, preferably 100/200.
It is adjusted in the range of 5-100 / 100. If the amount of the adhesive (binder) added is large, the pores between the particles become small, and the ink absorption speed becomes slow or the ink absorption amount is undesirably reduced. On the other hand, if the amount of the adhesive (binder) is too small, the strength of the recording layer may decrease, or in an extreme case, cracking may occur.

In general, since the dyes used in ink-jet inks are anionic, when a recording layer containing a pigment as a main component is selected, a cationic resin or a cationic compound such as alumina sol is added as a fixing agent for the dye. It is desirable. As the cationic resin, for example, aliphatic primary, secondary, tertiary amines, aliphatic unsaturated amines, aliphatic amines such as alicyclic amines, polyalkylene polyamines such as polyethylene amine and polypropylene polyamine, or derivatives thereof, Various commercially available cation resins such as an acrylic resin having a tertiary amino group or a quaternary ammonium group are exemplified. The amount of the cationic compound to be added is adjusted in the range of 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts of the pigment.

In addition, various auxiliaries such as a dispersant, a thickener, an antifoaming agent, a coloring agent, an antistatic agent, and a preservative used in the production of general coated paper are appropriately added.

The recording layer may be composed of one layer, but a plurality of recording layers may be provided in order to increase the ink absorbency and the like. Although the coating amount of the recording layer is not particularly limited, the total coating amount of the recording layer is 3 to 60 g / m ² , preferably 10 g / m ² .
５０50 g / m ² . If you have multiple recording layers,
It is preferable that the layer containing the polymer type silane coupling agent of the present invention is at least a surface layer (the layer farthest from the support). The coating amount of this surface layer is 1 to 30 g / m
² , preferably 3 to 15 g / m ² .

Further, in order to obtain an ink jet recording medium suitable for photographic recording, the surface layer of the recording layer may be subjected to a gloss treatment. Examples of the glossing method include, for example, a method in which a recording layer is provided on a molding surface in advance and then transferred onto a support (if the support has a recording layer, the recording layer is used) to peel off the molding surface. After applying the recording layer thereon, it is possible to obtain a high gloss by a method in which the recording layer is brought into close contact with the molding surface while it is in a wet state, dried as it is, and then peeled off the molding surface.

The method of bonding the recording layer provided on the molding surface to the support (or another recording layer) is not particularly limited. Bonding is performed under pressure (5 to 150 kg / cm) and heat (30 to 100 kg / cm).
C) only, but more preferably the upper layer and / or the lower layer is steamed or water-coated so that the moisture content of the recording layer is 50 to 350% based on the absolute dry weight, and then pressed by a calender or the like. This is feasible.
Of course, it is possible to provide an intermediate layer (adhesive, pressure-sensitive adhesive, etc.) on the support in advance and to adhere the intermediate layer, but as a more effective method, the intermediate layer should be a recording layer having ink absorbency. That is. That is, the recording layer is coated on the support, bonded in a wet state, and then dried to be bonded.

Examples of the material used for the molding surface include cellophane, polyethylene, polypropylene, and the like having high surface smoothness.
Plastic films such as soft polyvinyl chloride, hard polyvinyl chloride, polyester, etc., papers such as polyethylene laminated paper, glassine paper, impregnated paper, vapor-deposited paper, flexible sheets such as metal foil, synthetic paper, and inorganic glass Drums and plates having a smooth surface such as metal, plastic and the like are appropriately used. In particular, a polymer film (polyethylene, polypropylene, polyester, or the like) or a metal drum having a highly smooth surface is preferable from the viewpoints of the manufacturing process and the suitability for peeling the molding surface and the recording layer.

The molded surface is preferably smooth for the purpose of imparting gloss, and the surface roughness of the molded surface (JIS B-060)
In 1), Ra is preferably 0.5 μm or less, more preferably Ra is 0.05 μm or less. In addition, it is also possible to give a texture such as semi-gloss tone or matte tone by controlling the surface roughness.

The molding surface may be left untreated. However, in order to control the adhesive force between the molding surface and the recording layer to be smaller than the adhesive force between the recording layer and the support (or another recording layer), the coating on the molding surface is controlled. It is possible to apply a compound having releasability, such as silicone or fluororesin, on the surface to be used.

Examples of the coater for coating the recording layer and the intermediate layer include various known coaters such as a die coater, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, and a curtain coater. Device.

[0049]

The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted thereto.
Unless otherwise specified, parts and% in the examples are solid contents excluding water, and represent parts by weight and% by weight, respectively.

[Silica Sol A] Synthetic amorphous silica having an average particle diameter of 3 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nipsi)
1, HD-2, primary particle diameter: 11 nm) after being pulverized and dispersed by a sand grinder, further pulverized and dispersed by a pressure homogenizer, and repeated the pulverization and dispersion operation of the sand grinder and the pressure homogenizer until the average particle diameter becomes 70 nm. , 8% aqueous dispersion was produced as a trial. Dispersion 1
In 00 parts, diallyl dimethyl ammonium chloride / acrylamide copolymer (trade name: PAS, manufactured by Nitto Boseki Co., Ltd.)
-J81), 10 parts were added, and the mixture was thickened and aggregated. The mixture was further pulverized and dispersed with a pressure homogenizer to give an average particle diameter of 15 parts.
A 10% aqueous dispersion of 0 nm silica was obtained.

Example 1 The following substances were charged into a flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. The mixture was stirred at 90 ° C. for 3 hours under a nitrogen atmosphere, and then the solvent was removed. After distilling off, a polymer type silane coupling agent A was obtained. [Polymer-type silane coupling agent A] 10 parts of γ-methacryloxypropyltrimethoxysilane (manufactured by Kanto Chemical Co., Ltd.) 2- (2'hydroxy-5-methylacryloxyethylphenyl) -2H-benzotriazole (Otsuka Chemical 65 parts of dimethylaminoethyl methacrylate quaternary product (manufactured by Kyoeisha Chemical Co., Ltd., light ester DQ-100) 65 parts4,4-azobis (isobutyronitrile) (manufactured by Kyoeisha Chemical Co., Ltd.) 6.6 parts, 2-methoxyethanol (Wako Pure Chemical Industries, special grade reagent) 160 parts

To silica sol A (silica content: 100 parts), 10 parts of a 10% aqueous solution of the polymer type silane coupling agent A prepared in advance is added, and the mixture is continuously stirred at 70 ° C. for 3 hours. A silica sol coated with the ring agent A was obtained. Then, 30 parts of PVA (manufactured by Kuraray Co., trade name: PVA-135H, degree of polymerization: 3500, degree of saponification: 99% or more) was mixed with 30 parts of solid content concentration 10
% Of a coating material, and a commercially available coated paper (manufactured by Oji Paper Co., Ltd., trade name: OK Coat, 12 g / m ²⁾
7.9 g / m ² ) and dried to produce an ink jet recording medium of the present invention.

Example 2 A polymer type silane coupling agent B was obtained in the same manner as in Example 1 except that the following substances were used. [Polymer-type silane coupling agent B] 10 parts of γ-methacryloxypropyltrimethoxysilane 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (trade name: ADK STAB LA-, manufactured by Asahi Denka Kogyo KK) 82) 46 parts ・ Dimethylaminoethyl methacrylate quaternary compound 46 parts ・ 4,4-azobis (isobutyronitrile) 6.6 parts ・ 2-methoxyethanol 160 parts

A silica sol coated with the polymer type silane coupling agent B was obtained in the same manner as in Example 1 except that the polymer type silane coupling agent B was used instead of the polymer type silane coupling agent A. Subsequently, coating and drying were carried out in the same manner as in Example 1 to produce an ink jet recording medium of the present invention.

Example 3 A polymer type silane coupling agent C was obtained in the same manner as in Example 1 except that the following substances were used. [Polymer silane coupling agent C] 10 parts of γ-methacryloxypropyltrimethoxysilane 2,2,6,6-tetramethyl-4-piperidyl methacrylate (trade name: ADK STAB LA-87, manufactured by Asahi Denka Kogyo Co., Ltd.) 45 parts ・ Dimethylaminoethyl methacrylate quaternary compound 45 parts ・ 4,4-azobis (isobutyronitrile) 6.6 parts ・ 2-methoxyethanol 160 parts

A silica sol coated with the polymer type silane coupling agent C was obtained in the same manner as in Example 1 except that the polymer type silane coupling agent C was used instead of the polymer type silane coupling agent A. Subsequently, coating and drying were carried out in the same manner as in Example 1 to produce an ink jet recording medium of the present invention.

<Example 4> A polymer type silane coupling agent D was obtained in the same manner as in Example 1 except that the following substances were used. [Polymer silane coupling agent D] 10 parts of γ-methacryloxypropyltrimethoxysilane 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (trade name: ADK STAB LA- manufactured by Asahi Denka Kogyo Co., Ltd.) 82) 46 parts ・ 4,4-azobis (isobutyronitrile) 6.6 parts ・ 2-methoxyethanol 160 parts

A solid content concentration of 10 parts obtained by mixing 100 parts of silica sol A and 30 parts of PVA (manufactured by Kuraray Co., trade name: PVA-135H, degree of polymerization: 3500, degree of saponification: 99% or more)
% Of a coating material, and a commercially available coated paper (manufactured by Oji Paper Co., Ltd., trade name: OK Coat, 12 g / m ²⁾
After coating and drying at 7.9 g / m ² ), 5 g of a 10% methanol solution of the polymer type silane coupling agent D was applied.
/ M ² and then impregnated and dried to produce an ink jet recording medium of the present invention.

<Comparative Example 1> Silica sol A was treated with PVA (trade name: PVA, manufactured by Kuraray Co., Ltd.) without treatment with a silane coupling agent.
A-135H, degree of polymerization: 3500, degree of saponification: 99% or more) to prepare a coating material having a solid content of 10%, and the coating amount was adjusted to 20 g / m ² using the coating material. Commercially coated paper (manufactured by Oji Paper Co., Ltd., trade name: OK coated, 12
7.9 g / m ² ) and dried to produce an ink jet recording medium.

Comparative Example 2 A cationic polymer A was obtained in the same manner as in Example 1 except that the following substances were used. [Cationic polymer A]-2- (2'hydroxy-5-methylacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., trade name: RUVA-93) 65 partsDimethylaminoethyl methacrylate quaternary compound ( Produced by Kyoeisha Chemical Co., Ltd., trade name: Light Ester DQ-100) 65 parts ・ 4,4-azobis (isobutyronitrile) 6.6 parts ・ 2-methoxyethanol 160 parts

100 parts of silica sol A, 10 parts of an aqueous solution of cationic polymer A and PVA (manufactured by Kuraray Co., trade name: PV
A-135H, degree of polymerization: 3500, degree of saponification: 99% or more) to prepare a coating material having a solid content of 10%, and the coating amount was adjusted to 20 g / m ² using the coating material. Commercially coated paper (manufactured by Oji Paper Co., Ltd., trade name: OK coated, 12
7.9 g / m ² ) and dried to produce an ink jet recording medium.

Comparative Example 3 A cationic polymer B was obtained in the same manner as in Example 1 except that the following substances were used. [Cationic polymer B] • 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB LA-82) 46 parts • Dimethylaminoethyl methacrylate quaternary product 65 parts 6.6 parts of 4,4-azobis (isobutyronitrile) 160 parts of 2-methoxyethanol

100 parts of silica sol A, 10 parts of a cationic polymer B aqueous solution and PVA (manufactured by Kuraray, trade name: PV
A-135H, degree of polymerization: 3500, degree of saponification: 99% or more) to prepare a coating material having a solid content of 10%, and the coating amount was adjusted to 20 g / m ² using the coating material. Commercially coated paper (manufactured by Oji Paper Co., Ltd., trade name: OK coated, 12
7.9 g / m ² ) and dried to produce an ink jet recording medium.

The light fastness, recording density, and water fastness of the ink jet recording materials obtained in Examples and Comparative Examples were evaluated by the following methods, and are shown in Table 1.

[Light resistance] Ink jet printer (E
Using a PSON PM700C, a square figure with a side length of 2 cm is solid printed with magenta (M) (dedicated glossy paper mode), and the initial recording density of each color is measured using a Macbeth reflection densitometer (Macbeth, RD). -920), and the average of five measurements was calculated. Then, each sample was sampled using a xenon lamp type FADE-OMETER (A
TLAS ELECTRIC DEVICES Co.
(Model: CI35F, manufactured by Co., Ltd.) at 63 ° C. and 50% for 50 hours, and the recording density after exposure of each color was measured again with a Macbeth reflection densitometer. For each sample, the recording density residual ratio before and after the light irradiation treatment by the xenon lamp type FADE-OMETER was calculated using the following equation. Recording density residual rate (%) = recording density after processing / recording density before processing × 100

[Recording Density] Using an ink jet printer (PM700C manufactured by EPSON), the length of a side is 2c.
The m square figure was solid printed in black (Bk) (special glossy paper mode), and its recording density was measured with a Macbeth reflection densitometer. The numerical values shown in the table are average values of five measurements.

[Water resistance] Ink jet printer (E
Using PSON PM700C), a square figure with a side length of 2 cm is solid printed with magenta (M) (special glossy paper mode), dried for 24 hours, immersed in running water for 30 minutes, and eluted with ink Was visually determined. ：: Almost no bleeding △: Boundary of printed part bleeds ×: Almost ink is eluted

[0068]

[Table 1]

[0069]

As is apparent from Table 1, the ink jet recording medium containing the polymer type silane coupling agent of the present invention has excellent light fastness. Further, when a cationic monomer was contained as in Examples 1 to 3, the water resistance was also excellent. The reason why the ink jet recording medium containing the polymer silane coupling agent of the present invention is excellent in water resistance and light resistance is presumed as follows. Since the polymer type silane coupling agent of the present invention generates a silanol group by hydrolysis, it can be chemically bonded to the pigment surface. Further, it is also possible to form a three-dimensional network structure by condensation of silanol groups and insolubilize in water. Therefore, when incorporated in the ink receiving layer, the pigment surface can be effectively covered with a group having an ultraviolet absorbing ability and a light stabilizing function, and the dye can be protected from light. Further, when a cationic monomer is copolymerized in the polymer type silane coupling agent of the present invention, it is possible to fix an acid dye or a direct dye generally used in an inkjet recording ink, and Since the silane coupling agent itself is insoluble in water as described above, it does not elute even when the printed matter is immersed in water. That is, it has excellent water resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 11/00 C09D 11/00 F term (Reference) 2H086 BA34 4J002 BC111 BG071 BG131 BJ001 DE076 DE106 DE146 DE236 DJ006 DJ016 DJ036 FD096 GS00 4J039 AD22 EA35 EA38 GA24 4J100 AA02R AA03R AB02R AB07P AB07Q AB07R AC03R AC11R AE09R AG02R AG04R AG10R AJ01R AJ02R AJ08R AJ09R AL03R AL08P AL08Q AL08R AL09R AM15R AM19R AM21Q AN05P AN05Q AN05R AN13R AN14R AP01R AP16P AQ06R AQ08R AQ12R BA02R BA03Q BA03R BA05Q BA06Q BA08R BA12Q BA15Q BA22Q BA28P BA32P BA32R BA56R BA58Q BA77P BB01Q BC43Q BC45Q BC65Q BC66Q BC75Q CA05

Claims (5)

[Claims] 1. A polymer type silane coupling agent represented by the following general formula (1). -(X) a- (Y) b- (Z) c- General formula (1) In the above formula (1), X is a copolymerizable monomer having a group capable of producing a silanol group by hydrolysis. Y represents a repeating unit formed by polymerization of a copolymerizable monomer having a group having an ultraviolet absorbing function or a group having a light stabilizing function, and Z represents X, It represents a repeating unit formed by polymerization of a copolymerizable monomer having an ethylenically unsaturated group other than Y. a + b + c = 100
A is 10 to 90 mol% and b is 10 to 90 mol%
Mol% and c are 0 to 80 mol%. 2. The polymer-type silane coupling according to claim 1, wherein in the general formula (1), X is a repeating unit represented by the following general formula (2) or (3). Agent. Embedded image Embedded image However, in the general formulas (2) and (3), R
₁ , R ₂ and R ₃ are an alkyl group or an alkoxy group, and at least one of R ₁ , R ₂ and R ₃ is an alkoxy group. R ₄ is a methyl group or a hydrogen atom, and A is an oxygen atom or NH. J is a divalent linking group, and m
Is 0 or 1. 3. The polymer-type silane coupling according to claim 1, wherein in the general formula (1), Y is a repeating unit represented by the following general formula (4) or (5). Agent. Embedded image Embedded image However, in the general formulas (4) and (5), R
₄ , A, J and m have the same meanings as in the general formula (2). R ₅ is a hindered amine compound, a benzophenone compound,
A residue obtained by removing a hydrogen atom from a benzotriazole-based compound, a salicyl-based compound, or a phenol-based compound. 4. The polymer-type silane cup according to claim 1, wherein in the general formula (1), Z has one or more cationic groups selected from the following general formulas (6) to (8). Ring agent. Embedded image Embedded image Embedded image However, in the general formula (6), R ₄ , A, J and m have the same meaning as in the general formula (2), and in the general formulas (6) to (8), X ⁻ represents an anion. 5. An ink jet recording medium comprising the polymer type silane coupling agent according to claim 1.