JP2000109739A - Aqueous ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink composition inhibiting the deterioration of a pigment or a dye with UV light, persisting the effect over a long period, and giving sufficient light resistance, even when printed on a permeable substrate such as paper. SOLUTION: This aqueous ink composition is obtained by preparing an aqueous dispersion containing polymer particles having UV light-absorbing functional groups by a method, for example, comprising copolymerizing a monomer such as a (meth)acrylic monomer with a compound having a UV light-absorbing functional group, and subsequently adding at least one of a pigment or a dye to the prepared aqueous dispersion. The aqueous ink composition is further obtained by imparting a dispersion function to a pigment by the use of the polymer particles and subsequently similarly treating the pigment, etc. The weather resistance of the polymer particle themselves is improved by the employment of a polymer comprising at least one of an acrylic polymer, a polysiloxane and a fluorine-containing polymer as a polymer forming the polymer particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a printed material having excellent light fastness, in which the deterioration of pigments or dyes by ultraviolet rays is suppressed, and this effect is maintained for a long period of time. The present invention relates to an aqueous ink composition capable of obtaining sufficient light fastness even when printed on a certain base material. Further, in the present invention, by coating the pigment with a polymer having an ultraviolet absorbing performance, a dispersing function is imparted to the pigment, and the printed matter having excellent dispersibility of the pigment and better light resistance can be obtained. The present invention relates to an aqueous ink composition.

[0002]

2. Description of the Related Art Conventionally, when printing on paper or a substrate made of a synthetic resin film such as polyolefin or polyester, a printing ink containing an organic solvent has been used. However, printing inks containing such organic solvents have the danger of fire and explosion,
It is not preferable from the viewpoint of pollution and the like, and the transition to aqueous ink containing a small amount of organic solvent, preferably containing no organic solvent has been studied and has been put to practical use.

[0003] Generally, the performance of such a printing ink is as follows.
It depends on the binder contained in the ink, and the selection of the binder is important to obtain ink with excellent performance.
Various binders such as an emulsion type and a water-soluble type are provided in the aqueous ink, and a printed film having excellent adhesion and water resistance (characters formed after the ink is applied to a substrate and dried, (Meaning figures, patterns, etc.). However, even if a binder having such excellent performance is used, the problem of fading due to ultraviolet deterioration of the pigments and dyes as the colorant is unavoidable. It is blended.

As UV absorbers, general-purpose UV absorbers such as salicylic acid, benzophenone, benzotriazole, and cyanoacrylate have been used, all of which have poor compatibility with pigments, dyes and binders. The molecular weight is not too high. For this reason, there is a problem that bleed-out occurs with time and sufficient light resistance cannot be maintained for a long period of time. In the case of a permeable base material such as paper, the ultraviolet absorbent penetrates the paper etc. together with the water of the medium at the time of printing, and the printed coating film (the ink is printed on the base material and the coating before drying) is applied. ) Does not contain the required amount of ultraviolet absorber from the beginning, and as a result, there is a problem that the deterioration of the pigment or the like by ultraviolet rays is not sufficiently prevented, and the light resistance of the printed film is reduced.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems, and is intended to provide a permeable base material such as paper by incorporating a polymer having an ultraviolet absorbing property. Another object of the present invention is to provide a water-based ink composition capable of maintaining stable ultraviolet ray deterioration prevention performance over a long period of time and obtaining a printed matter having excellent light fastness. Further, the present invention provides a water-based ink composition capable of obtaining a printed matter having more excellent light fastness and the like by using a pigment coated with a polymer having an ultraviolet absorbing property and having an excellent dispersing function. The purpose is to provide.

[0006]

The aqueous ink composition of the first invention is characterized by containing a polymer having an ultraviolet absorbing functional group and at least one of a pigment and a dye. Further, the aqueous ink composition of the second invention is a composite comprising an acrylic polymer and at least one of a polysiloxane polymer and a fluorinated polymer,
And at least one of a pigment and a dye, wherein at least one of the acrylic polymer, the polysiloxane polymer, and the fluorinated polymer has an ultraviolet absorbing functional group. Features.

Further, the aqueous ink composition of the fourth invention is characterized in that it contains a pigment coated with a polymer having an ultraviolet absorbing functional group. Further, the aqueous ink composition of the fifth invention comprises an acrylic polymer, at least one of a polysiloxane polymer and a fluorine-containing polymer,
Comprising a pigment coated with a composite consisting of
At least one of the acrylic polymer, the polysiloxane polymer, and the fluorine-containing polymer has an ultraviolet absorbing functional group.

In the aqueous ink compositions of the first to third inventions, the polymer or composite functions as a pigment binder. The ink composition comprises an aqueous medium,
The main component is a polymer or composite particle dispersed in this medium, or a polymer or composite dissolved in this medium, and at least one of a pigment and a dye. Further, in the aqueous ink compositions of the fourth to seventh inventions, the polymer or the composite imparts a dispersing function to the pigment, and at the same time, the polymer or the composite functions as a binder for the pigment. . The ink composition has as its main components an aqueous medium and a polymer or composite particle dispersed in the medium or a pigment coated with a polymer or composite dissolved in the medium. The term “coated” may refer to a state in which the polymer or the composite is physically adsorbed on the pigment, or a state in which the polymer or the composite is chemically bonded by an ionic bond, a covalent bond, or the like. In the fourth to seventh inventions, a surfactant or a water-soluble polymer such as polyvinyl alcohol which is generally used as a pigment dispersant may be used in combination as a dispersant. Further, since the polymer or the composite functions as a binder, a commonly used binder is not required, but may be used in combination.

In the first and fourth aspects of the present invention, the "polymer having an ultraviolet absorbing functional group" may be used in the production of a polymer to produce a monomer such as an acrylate ester or a methacrylate ester (hereinafter referred to as "base monomer"). ) And a monomer having an ultraviolet-absorbing functional group [(hereinafter, among these monomers, especially acrylic monomers (which also mean acids and esters and methacrylic monomers) Is referred to as “UV-absorbing monomer a”.] In this manner, the UV-absorbing functional group is chemically bonded to the polymer. In particular, since they are bonded by a covalent bond, they do not bleed out as in the case of a general ultraviolet absorber compounded as a compound, and the ultraviolet deterioration of pigments and dyes is prevented and formed over a long period of time. Excellent light fastness of the printing film is stably maintained.

In the second and fifth inventions, the above “complex” can be prepared by the following method or the like. An acrylic monomer as a base monomer and a UV absorbing monomer a are copolymerized, and a polymerizable silane compound is condensed in the presence of the copolymer. In the presence of an acrylic polymer having or not having an ultraviolet absorbing functional group, a monomer having an ultraviolet absorbing functional group and capable of undergoing a condensation reaction with silanol (hereinafter, referred to as “UV absorbing monomer b”). ) Is co-condensed with the polymerizable silane compound in the step of producing the polysiloxane polymer. In the presence of a polysiloxane polymer having or not having an ultraviolet absorbing functional group, an acrylic monomer is polymerized,
Alternatively, the acrylic monomer and the UV absorbing monomer a are copolymerized.

An acrylic monomer is polymerized in the presence of a fluorine-containing polymer having or not having an ultraviolet absorbing functional group, or an acrylic monomer and a UV absorbing monomer a are copolymerized. . An acrylic monomer is polymerized in the presence of a fluorine-containing polymer having or not having an ultraviolet absorbing functional group, and a polymerizable silane compound and a UV absorbing monomer b are co-condensed. In the presence of a fluorine-containing polymer having or not having an ultraviolet absorbing functional group, an acrylic monomer and a UV absorbing monomer a are copolymerized, and a polymerizable silane compound and a UV absorbing monomer and b. According to any of these methods, similarly to the first and fourth inventions, the deterioration of the pigments and dyes by ultraviolet rays is prevented for a long period of time, and the excellent light fastness of the printed film is stably maintained.

Examples of the UV-absorbing monomer a include p-methacryloyloxyphenyl salicylate, 2-hydroxy-4-methacryloyloxybenzophenone,
(2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2- (2 ′
-Hydroxy-5'-methacryloyloxyethyl-
3'-tert-butylphenyl) -2H-benzotriazole and the like can be used. Further, as the UV absorbing monomer b, 2,4-dihydroxyphenyl salicylate, 2,4-dihydroxybenzophenone,
2'-dihydroxy-4-methoxybenzophenone, 3
-[3- (2H-benzotriazol-2-yl) -5
-Tert-butyl-4-hydroxyphenyl] propanol, ethyl-α-cyano-β, β-di (p-hydroxyphenyl) acrylate and the like can be used.

As described above, each of the UV-absorbing monomers a and b has a UV-absorbing functional group such as a salicylic acid-based, benzophenone-based, benzotriazole-based, or cyanoacrylate-based, The prevention performance prevents UV deterioration of pigments and dyes. These UV-absorbing monomers a and b may be used alone or in combination of two or more. In addition, among these UV-absorbing monomers a and b, or other monomers having an ultraviolet-absorbing functional group, by using a monomer copolymerizable with a fluorinated monomer, A fluorinated polymer having an ultraviolet absorbing functional group can be obtained.

The UV-absorbing monomer a is 0.5 to 60 when the total amount of the monomer and the acrylic monomer is 100 parts by weight (hereinafter simply referred to as “parts”). Parts, particularly preferably 1 to 50 parts, more preferably 2 to 40 parts.
Further, the UV-absorbing monomer b is 0 to 80 when the total amount of the monomer and the polymerizable silane compound is 100 parts.
Parts, particularly preferably 0 to 60 parts, more preferably 0 to 40 parts. Further, the total amount of monomers having an ultraviolet absorbing functional group, such as UV absorbing monomers a and b, when the polymer or composite having an ultraviolet absorbing functional group is 100 parts,
It is preferably 0.5 to 80 parts, particularly preferably 1 to 60 parts, and more preferably 2 to 40 parts. If the amount of the UV-absorbing monomers a and b or other monomers having an ultraviolet-absorbing functional group is too small, stable light resistance cannot be obtained for a long period of time. Further, when the amount of the monomer having the ultraviolet absorbing functional group is excessive, stable polymerization may be difficult.

The polymer that functions as a pigment binder in the first invention and the polymer that imparts a dispersing function to the pigment and functions as a pigment binder in the fourth invention are:
A method in which a base monomer and a monomer having an ultraviolet absorbing functional group are emulsion-polymerized in water or an aqueous medium, a method in which these monomers are solution-polymerized, and then re-emulsified in an aqueous medium (hereinafter, referred to as an aqueous medium). , Simply referred to as “re-emulsification method”). This emulsion polymerization,
Using a radical polymerization initiator, the reaction can be carried out in a soap-free system or in the presence of an emulsifier. Further, when a highly water-soluble base monomer such as acrylic acid is used in a large amount of at least 7% by weight (hereinafter, simply referred to as “%”) of all monomers, particularly at least 15%. Is a method of adding and dissolving a neutralizing agent after emulsion polymerization, or adding water after solution polymerization,
An aqueous solution in which a polymer is dissolved can be obtained by a method such as removal of an organic solvent, and a pigment and / or a dye can be added to the aqueous solution, or a dispersing function can be imparted to the pigment by the polymer to obtain an aqueous ink composition. Things.

The following various monomers can be used as the base monomer. Methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate,
n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-butyl (Cyclo) alkyl (meth) acrylates such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl (meth) acrylate;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, Methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, p
Alkoxy (cyclo) alkyl (meth) acrylates such as -methoxycyclohexyl (meth) acrylate;

Unsaturated epoxy compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, methyl glycidyl methyl acrylate and epoxidized cyclohexyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate; Fluoroalkyl (meth) acrylates such as fluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, and pentadecafluorooctyl (meth) acrylate;

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) diacrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate A) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 2,2′-bis [4- (meth)
Acryloxypropoxyphenyl] propane, 2,
Multifunctional (meth) acrylates such as 2'-bis [4- (meth) acryloxydiethoxyphenyl] propane, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate Kind;

Styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 3,4-dimethylstyrene, 4-methoxystyrene, -Ethoxystyrene, 2-chlorostyrene, 3-
Chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 4-chloro-
Aromatic vinyl compounds such as 3-methylstyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylpyridine and 4-vinylpyridine;

Unsaturated monomer containing a cyano group such as (meth) acrylonitrile, crotonitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate and cinnamate nitrile Body; vinyl chloride, vinylidene chloride,
Vinyl halide compounds such as fatty acid vinyl esters;
1,3-butadiene, isoprene, chloroprene, 2,
Conjugated dienes such as 3-dimethyl-1,3-butadiene;
Polymerizable silicones such as γ- (meth) acryloxypropyltrimethoxysilane, Silaplane FM0711 (trade name) manufactured by Chisso; 1,2,2,6,6-
Pentamethyl-4-piperidyl (meth) acrylate,
Polymerizable hindered amine light stabilizers such as 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate;

Hydroxymethyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth)
Acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxyamyl (meth) acrylate, 6
Hydroxy (cyclo) alkyl mono (meth) acrylates such as hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate;

Substituted hydroxy (cyclo) such as 3-chloro-2-hydroxypropyl (meth) acrylate and 3-amino-2-hydroxypropyl (meth) acrylate
Alkyl mono (meth) acrylates; glycerin mono- or di- (meth) acrylate, trimethylolpropane mono- or di- (meth) acrylate, pentaerythritol mono-, di- or tri- (meth) acrylate, etc. Free hydroxyl group-containing (meth) acrylates of trihydric or higher polyhydric alcohols: N-methylol (meth)
N-methylolated unsaturated carboxylic amides such as acrylamide, N, N-dimethylol (meth) acrylamide;

Aminoalkyl group-containing (meth) such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate Acrylates; 2
Acrylamides containing an aminoalkyl group such as -dimethylaminoethylacrylamide, 2-diethylaminoethylacrylamide, 2-dimethylaminopropylacrylamide, 3-dimethylaminopropylacrylamide; 2- (dimethylaminoethoxy) ethyl (meth) acrylate, 2- ( Aminoalkoxyalkyl group-containing (meth) acrylates such as diethylaminoethoxy) ethyl (meth) acrylate and 3- (dimethylaminoethoxy) propyl (meth) acrylate;

(Meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, monomethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl itaconate Carboxyl group-containing unsaturated monomers such as mono-2- (meth) acryloyloxyethyl xahydrophthalate or anhydrides thereof; (meth) acrylamide, N
-Methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethoxymethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylamide, maleic Amides or imides of unsaturated carboxylic acids such as acid amides and maleimides;

N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, N-
iso-propylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N,
N-di (n-propyl) acrylamide, N, N-di (iso-propyl) acrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N, N-di (n-propyl) methacrylamide ,
N-monoalkyl (meth) acrylamides having 1 to 10 carbon atoms in an alkyl group such as N, N-di (iso-propyl) methacrylamide; N, N-dialkylacrylamides;

(Meth) acrolein, crotonaldehyde, formylstyrene, formyl-α-methylstyrene, diacetoneacrylamide, (meth) acrylamidopivalinaldehyde, 3- (meth) acrylamidomethyl-anisaldehyde, and the following formula (1) Ethylenically unsaturated compounds having an ald group such as β- (meth) acryloyloxy-α, α-dialkylpropanal represented by

[0028]

Embedded image [In this formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₃
Represents an alkyl group having 1 to ₃ carbon atoms, and R ₄ represents an alkyl group having 1 to ₄ carbon atoms. ]

Diacetone (meth) acrylamide, 4 to
Vinyl alkyl ketones having 7 carbon atoms (vinyl methyl ketone, vinyl ethyl ketone, vinyl-n-propyl ketone, vinyl-iso-propyl ketone, vinyl-n-butyl ketone, vinyl-iso-butyl ketone, vinyl-tert- Butyl ketone), vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone,
Diacetone (meth) acrylate, acetonitrile (meth) acrylate, 2-hydroxypropyl (meth) acrylate-acetyl acetate, 3-hydroxypropyl (meth) acrylate-acetyl acetate, 2-
Hydroxybutyl (meth) acrylate-acetyl acetate, 3-hydroxybutyl (meth) acrylate-
Acetyl acetate, 4-hydroxybutyl (meth) acrylate-acetyl acetate, butanediol-
Ethylenically unsaturated compounds having a keto group, such as 1,4- (meth) acrylate-acetyl acetate;

Of these, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, styrene, α-methylstyrene, (meth) acrylonitrile, 1,3-butadiene, isoprene, γ- (meth) acryloxypropyltrimethoxy Silane, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono- or di-
(Meth) acrylate, (meth) acrylamide, N-
Methylol (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylic acid, diacetone (meth) acrylamide and the like are preferable.

Examples of the radical polymerization initiator include an oxidizing agent comprising an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, a sugar-containing iron pyrophosphate formulation, a sulfoxylate formulation, A redox initiator in combination with a reducing agent such as a sugar-containing iron pyrophosphate and sulfoxylate mixed formulation can be used. Further, persulfates such as potassium persulfate and ammonium persulfate can also be used.

Further, azo compounds such as azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2-carbamoylazaisobutyronitrile, benzoyl peroxide, lauroyl peroxide,
Organic peroxides such as tert-butylperoxy-2-ethylhexanoate can also be used. As the radical polymerization initiator, a redox initiator and a persulfate are particularly preferable. The amount of the radical polymerization initiator to be used is generally 0.05 to 5 parts, particularly preferably 0.1 to 2 parts, when the total amount of the monomers used is 100 parts.

As the emulsifier, any of an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier and the like can be used. Is preferred.

Examples of the anionic emulsifier include higher alcohol sulfate, alkylbenzene sulfonic acid, dialkyl succinate sulfonic acid, alkali metal salt of alkyl diphenyl ether disulfonic acid, and polyoxyethylene alkyl ether or sulfate of polyoxyethylene alkyl phenyl ether. And the like. Examples of the anionic reactive emulsifier include “Latemul S-180A” (trade name, manufactured by Kao Corporation), “Eleminol JS-2” (trade name, manufactured by Sanyo Chemical Co., Ltd.), and (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. "AQUALON HS-10", manufactured by Asahi Denka Kogyo Co., Ltd., trade name "Adecalia Soap SE-
10N "and the product name" Ant "manufactured by Nippon Emulsifier Co., Ltd.
ox MS-60 "can be used.

Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and the like. Further, as the nonionic reactive emulsifier, a trade name of "AQUALON RN-20" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a trade name of "Adekaria Soap NE-20" manufactured by Asahi Denka Kogyo Co., Ltd. and the like may be used. it can. Examples of the cationic surfactant include alkylpyridinyl chloride and alkylammonium chloride. As the amphoteric emulsifier, lauryl betaine is preferable.

The amount of the emulsifier used is usually 5 parts or less, particularly 0.1 to 4 parts, and more preferably 0.5 to 3 parts, when the total amount of the monomers used is 100 parts. Can be. Further, the emulsion polymerization is preferably performed in a soap-free system in order to form a printed film having excellent light resistance, and it is preferable to use a reactive emulsifier. In the emulsion polymerization, a radical transfer initiator, an emulsifier, a chain transfer agent, an electrolyte, a pH adjuster, and the like are blended as necessary, and when the total amount of the monomers to be used is 100 parts, usually 100 parts ~ 5
Using 00 parts of water, the polymerization temperature is 5 to 100 ° C, preferably 40 to 100 ° C, more preferably 50 to 90 ° C, and the polymerization time is 0 to 100 ° C.
It can be performed under the conditions of 1 to 10 hours, particularly 2 to 8 hours.

The polymerization system of the emulsion polymerization is a batch system,
A method in which the monomer is divided or continuously supplied, a method in which the pre-emulsion of the monomer is divided or continuously added, a method in which these methods are combined stepwise, and the like can be adopted. In addition, particularly when using a base monomer having low water solubility, a pre-emulsion is prepared in advance by forcibly emulsifying all monomers, water and an emulsifier using a high-pressure homogenizer or an ultrasonic disperser. After that, the polymerization is preferably carried out by a batch method, a method of adding a pre-emulsion in a divided or continuous manner, or the like. In this case, the polymerization conversion rate is preferably 99% or more.

In the solution polymerization in the re-emulsification method, an organic solvent, a radical polymerization initiator and the like are used. Examples of the organic solvent include esters such as methyl acetate and ethyl acetate; Hydrocarbons, acetone, cyclohexanone, ketones such as methyl ethyl ketone, methanol, ethanol, alcohols such as isopropanol and 1,4-dioxane,
Ethers such as diethylene glycol monomethyl ether, tetrahydrofuran, N, N-dimethylformamide and the like can be used.

Examples of the radical polymerization initiator used in the solution polymerization include various kinds of radical initiators similar to those in the emulsion polymerization described above, and azo compounds and organic peroxides are particularly preferable. The amount of the radical polymerization initiator used in the solution polymerization is 1 to the total amount of the monomers used.
When it is 00 parts, it can be usually 0.1 to 20 parts, preferably 0.5 to 10 parts. In addition, a self-emulsifying function at the time of re-emulsification can be imparted by using a reactive emulsifier such as that used at the time of the emulsion polymerization in advance during the solution polymerization. In this case, the amount of the reactive emulsifier used can be usually 20 parts or less, particularly 15 parts or less, and further 10 parts or less, when the total amount of the monomers used is 100 parts. Further, in this solution polymerization, a chain transfer agent or the like can be used in combination with an organic solvent and a radical polymerization initiator, if necessary. In addition, this solution polymerization is carried out for 10 to 10
Using 100 parts of an organic solvent, the polymerization can be carried out at a polymerization temperature of 5 to 100 ° C, preferably 40 to 100 ° C, more preferably 50 to 90 ° C, and a polymerization time of 0.1 to 10 hours, particularly 2 to 8 hours. .

To the polymer solution obtained by the solution polymerization, water and, if necessary, a neutralizing agent, an emulsifier and the like are added, and the mixture is stirred with or without heating to re-emulsify the polymer solution, or Accordingly, the polymer solution is dropped into water to which a neutralizing agent, an emulsifier, etc. are added, and the mixture is stirred under heating or non-heating, and the polymer solution is re-emulsified. A dispersion can be formed. It is desirable that the organic solvent used in the solution polymerization be reduced from the dispersion by heating, steam distillation, or the like after re-emulsification, or substantially all of the organic solvent be removed. In addition, when a large amount of a water-soluble base monomer such as acrylic acid is used in a large amount, after emulsion polymerization, a method of dissolving by adding an alkali,
As described above, an aqueous solution in which this polymer is dissolved can be obtained by adding water and, if necessary, a neutralizing agent after the solution polymerization and removing the organic solvent.

Further, as for the polymer, a part of the base monomer is used to form a polymer emulsion by an emulsion polymerization method or a re-emulsification method. It can also be produced by emulsion polymerization of a monomer. The components used in this method, such as a monomer, a radical polymerization initiator, and optional emulsifiers and chain transfer agents, and polymerization conditions are the same as in the above-described emulsion polymerization method.

The average particle size of the polymer particles produced by the emulsion polymerization or re-emulsification method is from 0.001 to 0.
9 μm, especially 0.01 to 0.6 μm, and further 0.02 to
It is preferably 0.5 μm. It is difficult to produce a polymer particle having an average particle diameter of less than 0.001 μm. On the other hand, if the average particle diameter exceeds 0.9 μm, the polymer particles may precipitate and Stability decreases.

In the present invention, as in the second invention and the fifth invention, the acrylic polymer and at least one of a polysiloxane polymer and a fluorine-containing polymer are used. A complex in which at least one of a coalesced polymer, a polysiloxane polymer, and a fluorine-containing polymer has an ultraviolet absorbing functional group can be used. Such a complex is described, for example, in the following (1) to
The composite can be produced by the method of (3), and since the polysiloxane-based polymer and / or the fluorine-containing polymer coexist, the composite has excellent weather resistance and durability such as light resistance of a printed matter. The performance is further improved.

(1) Acrylic polymer particles having or not having an ultraviolet absorbing functional group dispersed in an aqueous medium, or acrylic polymer having or not having an ultraviolet absorbing functional group dissolved in an aqueous medium, After absorbing at least the polymerizable silane compound of the polymerizable silane compound and the UV-absorbing monomer b, the polymerization reaction proceeds. Note that the polymerizable silane compound and the UV-absorbing monomer b only need to be at least partially absorbed by the acrylic polymer. (2) In the presence of polysiloxane polymer particles having or not having an ultraviolet absorbing functional group dispersed in an aqueous medium,
At least the acrylic monomer among the acrylic monomer and the UV-absorbing monomer a is polymerized. (3) In the presence of a fluorine-containing polymer particle having or not having an ultraviolet absorbing functional group dispersed in an aqueous medium, at least an acrylic monomer of an acrylic monomer and a UV absorbing monomer a Allow the body to polymerize. In (3), a polymerizable silane compound or the like may be further blended and polymerized.

As the polymerizable silane compound, the following general formula (2): R _n Si (OR ′) _4-n (2) (wherein R is an organic group having 1 to 8 carbon atoms, and R ′ is a carbon number 1 to
5 alkyl groups or C 1-4 acyl groups, n is 0
It is an integer of 2. And an alkoxysilane represented by the following general formula (3): R ″ _m SiO _{(4-m) / 2} (3) (where R ″ is a substituted or unsubstituted monovalent hydrocarbon) Group, m
Is an integer of 0 to 3. A linear, branched or cyclic siloxane having a structural unit represented by formula (1) can be used, and an alkoxysilane represented by formula (2) is preferable.

Hereinafter, a case where alkoxysilanes are used as the polymerizable silane compound will be described. However, a polysiloxane polymer can be produced in the same manner when other polymerizable silane compounds are used.

In the general formula (2), R has 1 to 8 carbon atoms.
Examples of the organic group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-hexyl, and n-octyl. And an alkyl group such as a group. A γ-chloropropyl group, a γ-bromopropyl group, a 3,3,3-trifluoropropyl group, a γ-glycidoxypropyl group, a γ- (meth) acryloyloxypropyl group, a γ-mercaptopropyl group, Examples thereof include a γ-aminopropyl group, a vinyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group. still,
R may have a carbonyl group.

Further, as the alkyl group having 1 to 5 carbon atoms or the acyl group having 1 to 4 carbon atoms for R ′, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- -Butyl group, sec-butyl group, tert-
Examples thereof include a butyl group, an n-pentyl group, an acetyl group, a propionyl group, and a butyryl group.

Specific examples of such alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-
Propoxysilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , Is
o-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, i
So-butyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and 3,3,3-trifluoropropyltriethoxysilane No.

Further, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Examples thereof include silane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diethyldimethoxysilane.

Among these alkoxysilanes, dimethyldimethoxysilane, dimethyldiethoxysilane,
Iso-butyltrimethoxysilane and phenyltriethoxysilane are preferred. One of these alkoxysilanes may be used alone, or two or more thereof may be used in combination. The alkoxysilanes can be used in combination with a metal alkoxide containing titanium, aluminum, or the like, or a silane coupling agent.

The amount of the polymerizable silane compound to be used in the method (1) is preferably 0.1 to 500 parts, particularly preferably 0.5 to 250 parts when the acrylic polymer is 100 parts. If the amount of the polymerizable silane compound is less than 0.1 part, the effect of improving the light resistance and durability of the print film may not be obtained. Properties and the adhesion between the printed film and the substrate tend to be reduced.

The absorption of the polymerizable silane compound and the UV-absorbing monomer b into the acrylic polymer is carried out by adding the polymerizable silane compound or the like to the aqueous medium containing the polymer at once, dividedly or continuously. It can be carried out by sufficiently stirring. Further, if necessary, a polymerizable silane compound or the like can be dissolved in an organic solvent before use. In the method (1), the amount of the polymerizable silane compound absorbed by the acrylic polymer is usually 5% or more, particularly 10% or more, and more preferably 30% or more of the amount of the polymerizable silane compound used. It is preferable that Further, at a stage where the polymerizable silane compound or the like is not sufficiently absorbed, the pH of the reaction system is usually adjusted to prevent the polymerization reaction of the compound or the like from proceeding.
It is preferably adjusted to 4 to 10, particularly 5 to 9, and more preferably 6 to 8. The treatment temperature is usually 90 ° C. or lower, particularly 70 ° C. or lower, more preferably 50 ° C. or lower, and more preferably 0 to 3 ° C.
0 ° C., and the processing time is usually 5 to 180 minutes,
It is preferable to set it for about 20 to 60 minutes.

The polymerization temperature of the polymerizable silane compound or the like absorbed by the acrylic polymer is usually 30 ° C. or higher, especially 50 ° C.
~ 100 ° C, further 70 ~ 90 ° C, polymerization time 0.3 ~
It is preferably 15 hours, especially 1 to 8 hours. This polymerization reaction can be easily controlled by adjusting the number of carbon atoms or pH of R ′, in addition to the polymerization temperature and the polymerization time. it can.

The average particle diameter of the composite particles obtained by the method (1) is about 0.001 to 0.9 μm, particularly about 0.01 to 0.6 μm, and more preferably about 0.02 to 0.5 μm. Preferably, there is. By reducing the average particle size of the composite particles, the water resistance and the mechanical strength of the formed printed film are improved although the viscosity of the dispersion system is increased. Therefore, in applications where water resistance, mechanical strength, and the like are particularly important, the average particle size of the composite particles is set to 0.1.
It is preferable that the thickness be about 02 to 0.1 μm. The average particle diameter can be controlled within a predetermined range by appropriately adjusting the average particle diameter of the acrylic polymer particles, the absorption amount of the polymerizable silane compound, and the like.

Next, in the above method (2), the particles of the polysiloxane polymer dispersed in the aqueous medium are mixed with a polymerizable silane compound by using a homomixer or an ultrasonic mixer or the like to obtain an alkylbenzenesulfonic acid. Can be prepared by mixing and polymerizing in an aqueous solution of a strongly acidic emulsifier. At that time, the graft crosslinking agent can be co-condensed, if necessary, and the UV-absorbing monomer b can be co-condensed. As the polymerizable silane compound,
Examples include the alkoxysilanes represented by the general formula (2) and the siloxanes having the structural unit represented by the general formula (3), and particularly the cyclic silane represented by the general formula (3). Siloxanes are preferred.

In the cyclic siloxanes represented by the general formula (3), the substituted or unsubstituted monovalent hydrocarbon group for R ″ may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group. Groups, a vinyl group and a phenyl group, and groups obtained by substituting these hydrocarbon groups with a halogen atom, a cyano group, and the like. Specific examples of the cyclic siloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane.

The graft cross-linking agents which are co-condensed as required include p-vinylphenylmethyldimethoxysilane, 2- (m-vinylphenyl) ethylmethyldimethoxysilane, (m-vinylphenylmethyl) dimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (o-vinylphenyl)- 1,1,2-trimethyl-2,2-dimethoxydisilane, 1- (p-vinylphenyl) -1,1-diphenyl-3-ethyl-3,3
-Diethoxydisiloxane and the like.

Further, m-vinylphenyl- [3- (triethoxysilyl) propyl] diphenylsilane, [3-
(P-isopropenylbenzoylamino) propyl] phenyldipropoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclotetrasiloxane, allylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, etc. Can be mentioned.

Of these, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane and 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane are preferred, and p-vinylphenylmethyl Dimethoxysilane is particularly preferred. When the total amount of the polymerizable silane compound and the graft crossing agent is 100 parts, the amount of the graft crossing agent used is 0.1 to 50 parts, particularly 0.5 to 10 parts, and more preferably 0.5 to 5 parts. It is preferable to use a part.

The strongly acidic emulsifier used during the compounding of the polymerizable silane compound and the UV-absorbing monomer b and the polymerization acts as an emulsifier for the polymerizable silane compound and also serves as an initiator for the polymerization reaction of this compound. Things. The amount of the strongly acidic emulsifier used is usually 0.1 to 10 parts, preferably 0.5 to 5 parts, when the total amount of the polymerizable silane compound and the graft crosslinking agent is 100 parts. The amount of water used is determined by adding the total amount of the polymerizable silane compound and the graft crossing agent to 1
When it is set to 00 parts, it is usually 100 to 500 parts,
Preferably it is 200 to 400 parts. The condensation temperature is usually 5 to 100C.

Further, the polysiloxane polymer may have its molecular chain terminal blocked by a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group or the like. The average particle size of the particles of the polysiloxane polymer can be easily adjusted by controlling the amounts of the strongly acidic emulsifier and water, the polymerization temperature, and the degree of dispersion using a homomixer or an ultrasonic mixer. Can be. The particles of the polysiloxane-based polymer thus obtained can be used alone or in combination of two or more.

In this manner, particles of the polysiloxane polymer dispersed in the aqueous medium are formed, and at least one of the acrylic monomer and the UV-absorbing monomer a is used in the presence of the particles. Polymerizes. The amount of the acrylic monomer used in the method (2) is 5 to 500 parts, and particularly preferably 10 to 400 parts, when the polysiloxane polymer (solid content) is 100 parts. preferable. When the amount of the acrylic monomer is less than 5 parts, the processability such as print film forming property, the adhesion between the print film and the base material and the like tend to decrease, and when the amount exceeds 500 parts, In some cases, the excellent weather resistance and durability of the polysiloxane polymer may not be sufficiently exhibited.

The method (2) is preferably carried out by emulsion polymerization. In this emulsion polymerization, at least a radical polymerization initiator and an emulsifier are used. As the radical polymerization initiator, the same one as in the first invention can be used, and a redox initiator and an organic peroxide are particularly preferable. The amount of the radical polymerization initiator used is usually, when the total amount of the monomers used is 100 parts,
0.05 to 5 parts, preferably 0.1 to 2 parts. Further, as the emulsifier, a strong acidic emulsifier such as an alkylbenzene sulfonic acid used when producing a dispersion of a polysiloxane polymer is suitable, and if necessary, an emulsifier used in the first invention, Other emulsifiers can be used in combination.

Emulsion polymerization can be carried out in combination with a radical polymerization initiator, a strongly acidic emulsifier and, if necessary, an additional emulsifier, a chain transfer agent, various electrolytes and a pH adjuster. When the total amount of the monomers used is 100 parts, usually, 100 to 500 parts of water, a predetermined amount of a radical polymerization initiator is used, and the polymerization temperature is 5 to 100 ° C, preferably 50 to 90 ° C, The polymerization is performed under the conditions of a polymerization time of 0.1 to 10 hours. At this time, it is preferable that the acrylic monomer, the radical polymerization initiator, and the like be added directly, dividedly or continuously to the aqueous medium in which the particles of the polysiloxane polymer are dispersed, and then polymerized. Further, the polymerization conversion rate is preferably 99% or more.

The average particle size of the composite particles obtained by the method (2) is usually from 0.001 to 0.9 μm,
Especially 0.01 to 0.6 μm, further 0.02 to 0.5 μm
m is preferable. By using particles having an average particle diameter in this range, it is possible to form a printed film having excellent film-forming properties, maintaining the stability of the dispersion system, and having good physical properties. The average particle diameter can be adjusted by controlling the average particle diameter of the dispersion of the polysiloxane polymer within a predetermined range.

Further, in the above method (3), a vinylidene fluoride polymer can be preferably used as the fluorine-containing polymer. As the vinylidene fluoride polymer, a homopolymer or copolymer of vinylidene fluoride is used. In the vinylidene fluoride copolymer, monomers copolymerizable with vinylidene fluoride include fluorine-containing monoolefins such as vinyl fluoride, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene, and hexafluoroisobutylene. And the like. In addition, during the polymerization of the fluorine-containing polymer, UV
By copolymerizing the absorbing monomers a and b or another monomer having an ultraviolet absorbing functional group, a fluorinated polymer having an ultraviolet absorbing functional group can be obtained.

Examples of monomers copolymerizable with vinylidene fluoride include perfluoro (meth) acrylic acid, (cyclo) alkyl ester of perfluoro (meth) acrylic acid,
Fluorinated acrylic monomers such as fluoro (cyclo) alkyl esters of (meth) acrylic acid can be mentioned. Furthermore, monomers containing no fluorine, such as monoethylenically unsaturated monomers such as propylene, cyclohexyl vinyl ether and 2-hydroxyethyl vinyl ether, and aliphatic conjugated dienes such as butadiene, isoprene and chloroprene are exemplified. These copolymerizable monomers are:
Only the species may be used, or two or more species may be used in combination. Incidentally, the amount ratio of vinylidene fluoride in the copolymer of vinylidene fluoride is usually 50% or more.

Examples of the vinylidene fluoride-based polymer include binary copolymers such as vinylidene fluoride homopolymer, vinylidene fluoride / tetrafluoroethylene copolymer, and vinylidene fluoride / hexafluoropropylene copolymer. Terpolymers such as vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer are preferred. Further, a vinylidene fluoride / hexafluoropropylene binary copolymer and a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene terpolymer are particularly preferred. One of these vinylidene fluoride polymers may be used alone, or two or more thereof may be used in combination.

The composition ratio of each monomer in the vinylidene fluoride copolymer is as follows. Preferably, vinylidene is 50 to 90%, and tetrafluoroethylene or hexafluoropropylene is 50 to 10%. Furthermore, in the case of vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene terpolymer, vinylidene fluoride is 50 to 80%, tetrafluoroethylene is 10 to 40%, and hexafluoropropylene is 5 to 40%.
% Is preferable. In addition, the weight average molecular weight of this vinylidene fluoride polymer is usually 10,000 to 200,000.

The particles of the vinylidene fluoride polymer dispersed in the aqueous medium can be prepared by the following ordinary method. In the presence or absence of other monomers, a method of emulsion polymerization of vinylidene fluoride in an aqueous medium, in the presence or absence of other monomers, after solution polymerization of vinylidene fluoride, A method of inverting the phase of the obtained vinylidene fluoride polymer solution to an aqueous dispersion, in the presence or absence of other monomers, after precipitation polymerization of vinylidene fluoride, the obtained polymer particles are converted into an aqueous medium. And the like. Among these methods,
Is preferred because the obtained emulsion of the vinylidene fluoride polymer can be used as it is in the polymerization of the acrylic monomer in the next step.

The average particle size of the particles of the vinylidene fluoride polymer can be appropriately adjusted according to the desired average particle size of the aqueous ink composition, but is preferably 0.001 to 0.5 μm. More preferably, it is 0.01 to 0.3 μm. The particles of the vinylidene fluoride polymer thus obtained may be of one type alone or of two or more types.

In order to polymerize acrylic monomers and other necessary monomers in the presence of fluorine-containing polymer particles dispersed in an aqueous medium, an emulsion polymerization method is usually employed. The amount of the acrylic monomer used in the method (3) is
When the fluorine-containing polymer (solid content) is 100 parts,
The amount is 20 to 500 parts, and particularly preferably 40 to 300 parts. If the amount of the acrylic monomer or the like is less than 20 parts, the processability such as film forming property and the adhesion of the printed film to the base material tend to be reduced. If the amount exceeds 500 parts, excellent weather resistance and durability of the fluorinated polymer itself may not be sufficiently exhibited.

The emulsion polymerization is carried out using a radical polymerization initiator, with or without the addition of an emulsifier. As the radical polymerization initiator and the emulsifier to be used,
The same ones as in the invention can be used. The amount of the radical polymerization initiator to be used is usually 0.05 to 5 parts, preferably 0.1 to 2 parts, when the total amount of the monomers used is 100 parts. The amount of the emulsifier used is usually 5 parts or less when the total amount of the monomers used is 100 parts. Further, at the time of emulsion polymerization, a chain transfer agent, various electrolytes, a pH adjuster and the like can be used in combination with a radical polymerization initiator and an emulsifier, if necessary. The conditions of this emulsion polymerization are not particularly limited, and the polymerization is carried out at a polymerization temperature of 30 to 100 ° C. and a polymerization time of 1 to 30 hours using a radical polymerization initiator and an emulsifier in a predetermined quantitative ratio in an aqueous medium. be able to. Further, the polymerization conversion rate at that time is preferably 99% or more.

In the emulsion polymerization, the particles of the fluorinated polymer and the acrylic monomer can be added by the following various methods. (A) a method in which the whole amount of the monomer is added to the aqueous medium in which the particles of the fluoropolymer are dispersed, and (b) a method in which the monomer is added to the aqueous medium in which the particles of the fluoropolymer are dispersed. After the reaction is started by charging the parts, the remaining monomer is divided or continuously added, (c) the total amount of the monomer is divided or dispersed in an aqueous medium in which particles of the fluoropolymer are dispersed or A method of adding continuously, (d) a method of dividing or continuously adding particles of a fluorinated polymer while polymerizing a monomer in an aqueous medium, and the like.

Among these methods, the method (a) is particularly preferable. In the method (b), the acrylic monomer or the like initially charged is 5% of the total amount of the monomers used.
The method of making it 0% or more is preferable. Emulsion polymerization of an acrylic monomer or the like performed in the presence of a fluorine-containing polymer particle dispersed in an aqueous medium can be considered as one type of seed polymerization. Although the reaction behavior is not necessarily clear, it is considered that the added acrylic monomer or the like is mainly absorbed or adsorbed by the fluorinated polymer particles, and the polymerization proceeds while swelling the particles.

Accordingly, the existence form of each polymer component in the composite particles obtained by the method (3) is as follows:
A graft-bonding type of a fluorinated polymer and a (meth) acrylic polymer or the like, a core-shell type having a fluorinated polymer as a core, a (meth) acrylic polymer or the like as a shell, A homogeneous type in which a (meth) acrylic polymer or the like is uniformly mixed in a single particle, or a mixed type thereof can be considered. In particular, when importance is attached to the light resistance of a printed film, a homogeneous type is preferable. The homogeneity of the composite particles can be easily confirmed by showing a single glass transition point in differential scanning calorimetry.

The average particle diameter of the composite particles obtained by the method (3) is usually 0.001 to 0.9 μm,
Especially 0.01 to 0.6 μm, further 0.02 to 0.5 μm
m is preferable. This average particle size is 0.001
If it is less than μm, the viscosity of the dispersion increases, making it difficult to increase the solid content ratio, and depending on the use conditions, when a large mechanical shearing force is applied, coagulated matter is easily generated. On the other hand, when the average particle size exceeds 0.9 μm, the storage stability of the dispersion tends to decrease. This average particle diameter can be easily adjusted by controlling the average particle diameter of the particles of the fluoropolymer.

In the case where the pigment is provided with a dispersing function by a polymer having an ultraviolet absorbing functional group or a composite comprising a plurality of polymers as in the fourth to seventh inventions, the polymer or the polymer The weight average molecular weight of the polymer constituting the composite is preferably 3000 or more as in the sixth invention. This weight average molecular weight, especially 4000 or more,
More preferably, it is 5000 or more. When the weight average molecular weight of the polymer is less than 3000, the durability of the water resistance and light resistance of the formed printed film tends to be reduced. Further, the acid value of the polymer or the composite is preferably 30 mgKOH / g or more as in the seventh invention. This acid value is particularly preferably at least 40 mgKOH / g, more preferably at least 50 mgKOH / g. The acid value of the polymer or composite is 30 mg KOH /
When the amount is less than g, a sufficient dispersing function is not provided to the pigment, and the dispersion of the pigment may be insufficient.

In the present invention, when the acrylic polymer constituting the polymer or the composite comprises a monomer containing a carbonyl group-containing monomer, the polymer or the composite is a hydrazino group-containing crosslinking agent. May be crosslinked. The hydrazino group-containing cross-linking agent is a compound having two or more hydrazino groups in one molecule. Dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and the like. Further, the hydrazino group of at least a part of these polyfunctional hydrazine derivatives is reacted with carbonyl compounds such as acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, and diacetone alcohol. The compound blocked by the
It is referred to as "blocked polyfunctional hydrazine derivative". ),
For example, adipate dihydrazide monoacetone hydrazone, adipate dihydrazide diacetone hydrazone, and the like can also be used. By using such a blocked polyfunctional hydrazine derivative, the progress of the cross-linking reaction of the aqueous dispersion can be appropriately suppressed, so that the redispersibility, which is particularly important as an aqueous ink, can be further improved.

The hydrazino group-containing crosslinking agent can be blended in an appropriate step of preparing the aqueous ink composition. It can be blended during or after the production of the polymer, but in order to suppress the generation of coagulate during the production of the polymer and maintain the polymerization stability, the entire amount of the hydrazino group-containing cross-linking agent is added to the polymer. It is preferred to mix after production.

The compounding amount of the hydrazino group-containing crosslinking agent is such that the hydrazino group is usually used in an amount of 0.1 mol per mol of the carbonyl group contained in the carbonyl group-containing (meth) acrylic polymer.
10 to 10 mol, preferably 0.2 to 5 mol, particularly 0.5 to 3 mol, and more preferably 0.8 to 2 mol. When the amount ratio of the hydrazino group-containing cross-linking agent is less than 0.1 mol, the crosslinking effect is hardly obtained. is there.

The hydrazino group-containing crosslinking agent has an effect of forming a network structure by reacting the hydrazino group with the carbonyl group contained in the carbonyl group-containing (meth) acrylic polymer during the drying of the printed coating film. . At the time of this cross-linking reaction, usually, a catalyst may not be used, but a catalyst such as a water-soluble metal salt such as zinc sulfate, manganese sulfate, and cobalt sulfate may be optionally added.

The coloring agents such as pigments and dyes used in the aqueous ink compositions according to the first to third aspects of the present invention usually contain 1 to 100 parts by weight of the solid content of the polymer or composite having an ultraviolet absorbing functional group. １０００1000 parts by weight. The coloring agent used at this time may be any one that has been conventionally used in inks and the like, and inorganic pigments such as titanium oxide, alumina and carbon black, various azo pigments, phthalocyanine, and organic pigments such as hollow particles. Various dyes such as acid dyes, basic dyes, oil dyes, disperse dyes, and reactive dyes can be used. Further, these colorants may be simply added, and are physically adsorbed to the polymer or the complex,
Alternatively, they may be chemically bonded. Further, these colorants can be used alone or in combination of two or more.

The pigment used in the aqueous ink compositions of the fourth to seventh inventions is usually 1 to 10 parts by weight per 100 parts by weight of the solid content of the polymer or composite having an ultraviolet absorbing functional group.
00 parts by weight are used. About the kind, what is necessary is just what has been conventionally used for ink etc., and inorganic pigments, such as titanium oxide, alumina, and carbon black, various azo pigments, phthalocyanine, and organic pigments, such as hollow particles, can be used. , Or a mixture of two or more. The method of coating the pigment with the polymer or the complex is not particularly limited, for example, using the polymer or the complex as a polymer dispersant, using a mechanically dispersing method or a coupling agent, the pigment In general, the pigment can be coated by any method of coating a pigment, such as a method of modifying the surface with a polymer or a composite.

The following additives can be added to the aqueous ink composition of the present invention according to the purpose. As a light stabilizer for further improving the light fastness, a light stabilizer such as an organic nickel-based or hindered amine-based stabilizer conventionally used in an ink composition can be used. As the light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and tetraxy (2,2,6,6-
Hindered amine-based light stabilizers such as tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.

The amount of the light stabilizer is usually 10 parts by weight based on 100 parts of the solid content contained in the aqueous ink composition.
Parts or less, preferably 5 parts or less. If the compounding amount of the light stabilizer exceeds 10 parts, the surface of a print film formed using the aqueous ink composition may be stained.

Further, in order to improve the print film forming property and wettability, methyl alcohol, ethyl alcohol, n-
Propyl alcohol, iso-propyl alcohol, n
Alcohols such as -butyl alcohol, n-amyl alcohol, n-hexyl alcohol, methyl cellosolve,
Ethyl cellosolve, n-propyl cellosolve, iso-
Cellosolves such as propyl cellosolve, n-butyl cellosolve and n-hexyl cellosolve; carbitols such as methyl carbitol and ethyl carbitol; cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and tri-n-butoxymethyl phosphate And organic solvents such as phosphates. The compounding amount of these organic solvents is usually 50% or less, preferably 40% or less, more preferably 30% or less of the total amount of the aqueous ink composition.

In addition, an organic solvent that can be used as a humectant, such as glycols such as ethylene glycol, diethylene glycol, propylene glycol, and hexylene glycol, and glycerin can be added for the purpose of further supplementing redispersibility.

Further, as other additives, water-soluble or water-dispersible resins generally used as aqueous resins, for example, carboxylated aromatic vinyl such as polyester resin, epoxy resin, acrylic resin and styrene-maleic acid resin. Resin, urethane resin and the like can be used. In addition, an antifoaming agent, a thickener, a stabilizer against heat, a leveling agent, a lubricant, an antistatic agent, a dye, a pigment, a fungicide, and the like can also be used.

The aqueous ink compositions of the first to third inventions obtained as described above contain a polymer or a complex containing an ultraviolet-absorbing functional group. Can be suppressed. Moreover, these polymers and the like do not easily bleed out unlike ordinary ultraviolet absorbers, and thus the obtained printed matter can maintain excellent light fastness for a long period of time. Further, in this aqueous ink composition, when the substrate is permeable such as paper,
There is no problem that the ultraviolet absorber has penetrated the base material and the effect of preventing sufficient deterioration cannot be obtained. Furthermore, the fourth
In the aqueous ink compositions of the seventh to seventh aspects, since the pigment has a dispersing function by a polymer or a complex having an ultraviolet absorbing functional group, the light resistance of the printed matter can be more reliably improved. Therefore, as printing inks such as gravure and flexo, inks for writing implements, inks for OA equipment, and the like, the present invention can be applied to various printed materials such as paper, plastic molded products, films, glass, metals, and ceramics.

[0092]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples unless it exceeds the gist. The measurement of physical properties was performed by the following methods.

(1) Average particle size; dynamic light scattering type particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., model “LPA-310”
0 "). (2) Average molecular weight; gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, model “HLC-
8020 ") as measured by polystyrene. (3) Acid value: It was calculated by the following formula based on the molecular weight and the amount of the monomer having an acidic functional group used in the production of the polymer. Acid value (mgKOH / g) = Xa × 56 / Ma × 1000 where Xa: ratio of monomer having an acidic functional group contained in the total solid content, Ma; molecular weight of monomer having an acidic functional group , 56; molecular weight of KOH

(4) Light fastness: The aqueous ink composition was applied to a glass plate to form a 5 μm-thick coating film at 25 ° C. and 63
The specimen was left standing in an atmosphere of% RH for 24 hours to obtain a test piece. The initial color density of this test piece was measured by a Macbeth densitometer (manufactured by Macbeth, model “RD-1917”). After that, Xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.)
The test pieces were exposed to ultraviolet light for 20, 50 and 100 hours in an atmosphere of 63 ° C. and 70% RH using a black panel. Next, the color density of the test piece after the exposure was measured, and the retention with respect to the initial density was evaluated. The evaluation criteria are as follows. ◎: Retention of more than 90%, ○: Retention of 80 to 90%, Δ: Retention of 50 to 70%, ×: Retention of less than 50%.

(5) Water resistance: The aqueous ink composition was applied to a glass plate to form a coating film having a thickness of 5 μm,
The specimen was left standing in an atmosphere of% RH for 24 hours to obtain a test piece. The appearance of the coating film after immersing the test piece in distilled water at 20 ° C. for 24 hours was visually observed and evaluated. The evaluation criteria are as follows. A: No spots or swelling of the coating film are observed at all. ；: Some spots or swelling of the coating film are observed. ×: The coating film was dissolved and dropped off.

(6) Persistence of effect of light fastness: After testing the water fastness, the light fastness was evaluated again in the same manner as described above. Evaluation criteria are the same as in the case of light resistance. (7) Dispersion stability: The dispersion state of the aqueous ink composition was visually observed. The evaluation criteria are as follows. ；: Well dispersed, no separation or thickening. ×;
Poor dispersion. (8) Storage stability: After leaving the aqueous ink composition at 50 ° C. for one month, the state was visually observed. The evaluation criteria are as follows. ；: No change. ×: sedimentation, separation, thickening (solidification).

The pigment dispersion was prepared by adding 25 parts of water and a styrene-acrylic acid copolymer aqueous solution (trade name “Johncryl J-62”, manufactured by Johnson Polymer Co., Ltd.).
Part (in terms of solid content) is C.I. I. Pigment Yellow 17 was added with stirring, and the mixture was further mixed for 1 hour by a sand mill.

Synthesis Example 1 [Aqueous Dispersion (1-1)] In a stainless steel autoclave equipped with a stirrer, a thermometer, a heater, a monomer addition pump and a nitrogen gas introducing device, 100 parts of water was used as an initial component. , A reactive emulsifier (trade name “Latemul S-180A” manufactured by Kao Corporation; hereinafter,
It is called "reactive emulsifier". 2) (in terms of solids) and 0.5 part (in terms of solids) of a 5% aqueous solution of potassium persulfate were charged, the gas phase was purged with nitrogen gas for 15 minutes, and then the temperature was raised to 75 ° C.

Thereafter, as additional components, 50 parts of water, 1 part of a reactive emulsifier (in terms of solid content), and 2- (2'-hydroxy-5'-methacryloyloxyethyl, a monomer having an ultraviolet absorbing functional group, are used. Phenyl) -2H-benzotriazole (“RUVA” in Table 1) 5 parts,
Emulsion polymerization was performed at 80 ° C. while continuously adding the mixture of the types and the amounts of the monomers described in Table 1 over 3 hours, and after the addition was completed, the mixture was aged at 85 to 95 ° C. for 2 hours, 25
After cooling to ° C., the pH was adjusted to 8 with ammonia.

Then, 0.5 part of adipic acid dihydrazide (ADH) which is a polyfunctional hydrazine derivative (equivalent ratio of carbonyl group to hydrazino group based on keto group;
After the addition of 9), the mixture was stirred for about 1 hour, and filtered through a 200-mesh wire net to obtain an aqueous dispersion (1-1). The average particle diameter of the polymer particles contained in the aqueous dispersion (1-1) is 0.06 μm, the weight average molecular weight of the polymer is 10,000,000,
The acid value was 19 mgKOH / g.

Synthesis Example 2 [Aqueous Dispersion (1-2)] In the same autoclave as in Synthesis Example 1, RUVA2 was added.
Parts, a reactive emulsifier, 1 part, an aqueous dispersion (average particle diameter; 120 nm) of a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer (weight ratio; 60/25/15) which is a fluorine-containing polymer. (Solid content; 30%) 1
00 parts (in terms of solid content) and the type and amount of monomer shown in Table 1 ("RHALS" in Table 1 is 1, 2, 2,
2,6,6-pentamethyl-4-piperidyl methacrylate. )) And heated to 80 ° C.

Thereafter, a 5% aqueous solution of potassium persulfate was added in 0.1% aqueous solution.
Add 3 parts (in terms of solid content), polymerize at 85 to 90 ° C for 3 hours, cool to 25 ° C, and adjust the pH with diethanolamine.
Adjusted to 8. Next, the mixture was filtered through a 200-mesh wire net to obtain an aqueous dispersion (1-2). This aqueous dispersion (1-
The average particle size of the composite particles contained in 2) is 0.15 μm.
m, weight average molecular weight of polymer is 1,000,000, acid value is 8mg
KOH / g.

Synthesis Example 3 [Aqueous Dispersion (1-3)] In the same autoclave as in Synthesis Example 1, 200 parts of ethanol, 2 parts of 2,2′-azobisisobutyronitrile (in terms of solid content), And a mixture of monomers of the kind and blending amount shown in Table 1, and the gas phase was purged with nitrogen gas for 15 minutes, then heated to 60 ° C. and polymerized for 1 hour. afterwards,
The mixture was aged at 70 to 75 ° C. for further 4 hours, cooled to 25 ° C., and adjusted to pH 9 with ammonia. Next, the obtained polymer solution was gradually added to a mixed solution of 300 parts of water and 1 part of an emulsifier (trade name “HITENOL N-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) with stirring, and re-emulsification was performed. Performed to obtain an aqueous dispersion. Next, the whole amount of the aqueous dispersion was transferred to an eggplant-shaped flask, ethanol was removed by a rotary evaporator, and the resultant was filtered through a 200-mesh wire net to obtain an aqueous dispersion (l-3). The average particle size of the polymer particles contained in the aqueous dispersion (1-3) is 0.20 μm, the weight average molecular weight of the polymer is 5,000,000, and the acid value is 32 mgKOH /
g.

Synthesis Example 4 [Polymer aqueous solution (1-4)] In the same autoclave as in Synthesis example 1, 200 parts of ethanol, 4 parts of 2,2'-azobisisobutyronitrile (in terms of solid content), After charging 2 parts of n-octylthioglycol, which is a molecular weight regulator, and a mixture of monomers of the kind and compounding amount shown in Table 1, the gas phase was replaced with nitrogen gas for 15 minutes, and then heated to 60 ° C. And polymerized for 1 hour. afterwards,
After aging for 4 hours at 70 to 75 ° C and cooling to 25 ° C, the pH was adjusted to 9 with dimethylethanolamine. Next, 300 parts of water was added to the obtained polymer aqueous solution, and the whole amount was transferred to an eggplant-shaped flask, and ethanol was removed with a rotary evaporator to obtain a polymer aqueous solution (1-4). The polymer contained in the polymer aqueous solution (1-4) had a weight average molecular weight of 20,000 and an acid value of 184 mgKOH / g.

Synthesis Example 5 [Aqueous Dispersion (1-5)] In an autoclave similar to that of Synthesis Example 1, 100 parts of water, 0.5 part of a reactive emulsifier, and a 5% aqueous solution of potassium persulfate were used as initial components. 0.4 parts were charged, and the gas phase was purged with nitrogen gas for 15 minutes, and then heated to 75 ° C. Thereafter, as an additional component, 50 parts of water, 1 part of a reactive emulsifier, and a mixture of monomers of the type and blending amount shown in Table 1 were continuously added over 3 hours to carry out emulsion polymerization at 80 ° C. After completion of the addition, the mixture was aged at 85 to 95 ° C for 2 hours, cooled to 25 ° C, and adjusted to pH 8 with ammonia to obtain an aqueous dispersion.

Next, 10 parts of methyltriethoxysilane was added to the aqueous dispersion, and the mixture was stirred at 25 ° C. for about 1 hour.
After absorbing methyltriethoxysilane to the polymer contained in the aqueous dispersion, the temperature was raised to 70 ° C., and condensation was performed for 3 hours.
An aqueous dispersion containing composite particles in which the acrylic polymer and the polysiloxane coexist in the same particle was obtained. Then 25
C., and 1.2 parts of ADH (equivalent ratio of carbonyl group to hydrazino group based on keto group; 1.1) was added,
After stirring for about 1 hour, the mixture was filtered through a 200-mesh wire net to obtain an aqueous dispersion (1-5). This aqueous dispersion (1-
The average particle diameter of the composite particles contained in 5) is 0.08 μm,
The polymer has a weight average molecular weight of 1,000,000 and an acid value of 44 mgK.
It was 0H / g.

Synthesis Example 6 [Aqueous polymer solution (1-6)] An aqueous polymer solution (1-6) was prepared in the same manner as in Synthesis example 4 except that the monomers used in the polymerization were changed as shown in Table 1. I got The polymer contained in the aqueous polymer solution (1-6) had a weight average molecular weight of 3,000 and an acid value of 118 mgKOH /
g. Synthesis Example 7 [Aqueous dispersion (1-7)] An aqueous dispersion (1-7) was obtained in the same manner as in Synthesis example 1 except that the monomers used in the polymerization were changed as shown in Table 1. . The average particle diameter of the polymer particles contained in the aqueous dispersion (1-7) was 0.10 μm, the weight average molecular weight of the polymer was 200,000, and the acid value was 50 mgKOH / g. The results are shown in Table 1.

Synthesis Example 8 [Aqueous Dispersion (2-1)] An aqueous dispersion (2-1) was prepared in the same manner as in Synthesis Example 1 except that the monomers used in the polymerization were changed as shown in Table 2. I got The average particle diameter of the polymer particles contained in the aqueous dispersion (2-1) was 0.05 μm, the weight average molecular weight of the polymer was 8,000,000, and the acid value was 28 mgKOH / g. Synthesis Example 9 [Aqueous dispersion (2-2)] An aqueous dispersion (2-2) was obtained in the same manner as in Synthesis example 6, except that the monomers and the like used in the polymerization were changed as shown in Table 2. . The average particle diameter of the polymer particles contained in the aqueous dispersion (2-2) is 0.40 μm, and the weight average molecular weight of the polymer is 2
Million, the acid value was 19 mgKOH / g.

Synthesis Example 10 [Aqueous dispersion (2-3)] An aqueous dispersion (2-3) was prepared in the same manner as in Synthesis example 6, except that the monomers used in the polymerization were changed as shown in Table 2. I got The average particle size of the polymer particles contained in the aqueous dispersion (2-3) was 0.07 μm, the weight average molecular weight of the polymer was 900,000, and the acid value was 19 mgKOH / g. Synthesis Example 11 [Polymer aqueous solution (2-4)] Synthesis Example 4 except that the monomers used in the polymerization were changed as shown in Table 2.
In the same manner as in the above, a polyhydrate aqueous solution (2-4) was obtained. The polymer contained in this polymer aqueous solution (2-4) had a weight average molecular weight of 2,000 and an acid value of 173 mgKOH / g.

Synthesis Example 12 [Aqueous dispersion (2-5)] An aqueous dispersion (2-5) was prepared in the same manner as in Synthesis example 1 except that the monomers used in the polymerization were changed as shown in Table 2. I got The average particle diameter of the polymer particles contained in the aqueous dispersion (2-5) was 0.065 μm, the weight average molecular weight of the polymer was 25,000, and the acid value was 25 mgKOH / g. Table 2 shows the above results.

[0111]

[Table 1]

[0112]

[Table 2]

Example 1 10 parts (in terms of solids) of the aqueous dispersion (1-1) obtained in Synthesis Example 1, 25 parts (in terms of solids) of a pigment dispersion, 5 parts of isopropyl alcohol and 60 parts of water were mixed. Then, the mixture was filtered through a 200 mesh wire net to obtain an aqueous ink composition. Example 2 An aqueous ink composition was obtained in the same manner as in Example 1, except that the aqueous dispersion (1-2) obtained in Synthesis Example 2 was used.

Example 3 15 parts (in terms of solid content) of the aqueous dispersion (1-3) obtained in Synthesis Example 3 were mixed with C.I. I. 20 parts of Acid Yellow 23, 5 parts of isopropyl alcohol and 6 parts of water
0 parts were mixed and filtered through a 200 mesh wire net to obtain an aqueous ink composition. Example 4 To 15 parts (in terms of solid content) of the aqueous polymer solution (1-4) obtained in Synthesis Example 4, 60 parts of water and 5 parts of isopropyl alcohol, C.I. I. Pigment Yellow 1
7 were added with stirring. These were further mixed for 1 hour by a sand mill, and then filtered through a 200-mesh wire net to obtain an aqueous ink composition.

Example 5 Using the aqueous dispersion (1-5) obtained in Synthesis Example 5, an aqueous ink composition was obtained in the same manner as in Example 4. Example 6 An aqueous ink composition was obtained in the same manner as in Example 4, except that the aqueous polymer solution (1-6) obtained in Synthesis Example 6 was used. Example 7 An aqueous ink composition was obtained in the same manner as in Example 4 using the aqueous dispersion (1-7) obtained in Synthesis Example 7. Table 3 shows the above results.

Comparative Example 1 An aqueous ink composition was obtained in the same manner as in Example 1 except that the aqueous dispersion (2-1) obtained in Synthesis Example 8 was used. Comparative Example 2 An aqueous ink composition was obtained in the same manner as in Example 1 except that the aqueous dispersion (2-2) obtained in Synthesis Example 9 was used. Comparative Example 3 An aqueous ink composition was obtained in the same manner as in Example 3, except that the aqueous dispersion (2-8) obtained in Synthesis Example 10 was used.

Comparative Example 4 Using the polymer aqueous solution (2-4) obtained in Synthesis Example 11,
An aqueous ink composition was obtained in the same manner as in Example 4. Comparative Example 5 An aqueous ink composition was obtained in the same manner as in Example 4 using the aqueous dispersion (2-5) obtained in Synthesis Example 12. Table 4 shows the above results.

[0118]

[Table 3]

[0119]

[Table 4]

According to the results shown in Table 3, with the aqueous ink compositions of Examples 1 and 2, a film having excellent light resistance, water resistance, and durability of light resistance was formed, and dispersion stability and storage stability were observed. Is also good. Further, according to the composition of Example 2 in which composite particles comprising an acrylic polymer and a fluorine-containing polymer are used, a film having particularly excellent water resistance is formed. Furthermore, since the composition of Example 3 is a dye-based composition, although the light resistance of a film formed is slightly inferior to that of a pigment-based composition,
As a dye system, it has sufficient light fastness, a film with excellent water and light fastness effect durability is formed, dispersion stability,
Good storage stability.

Further, in the compositions of Examples 4 to 7, the dispersion function was imparted to the pigment by the polymer having a Shiba-ray absorbing functional group. An excellent film is formed, and the dispersion stability and storage stability are also good. However, in Example 6, since the weight average molecular weight of the polymer was slightly small at 3000, the durability of the light resistance effect was slightly inferior to the others. Furthermore, in Example 5, since composite particles composed of an acrylic polymer and polysiloxane were used, a film having particularly excellent water resistance was formed.

On the other hand, according to the results in Table 4, Comparative Examples 1 to 3
In this case, since the polymer particles do not contain an ultraviolet absorbing functional group, both pigments and dyes are inferior in light resistance. In Comparative Example 2, the average particle size of the polymer particles was 0.3 μm.
m and poor storage stability. Furthermore, in Comparative Examples 4 and 5, since the pigment has a dispersing function by a polymer containing no ultraviolet absorbing functional group, the formed film is inferior in light resistance. In Comparative Example 4,
Since the weight average molecular weight of the polymer was less than 3,000, the water resistance was poor, and the durability of the light resistance effect could not be evaluated. Further, in Comparative Example 5, the acid value of the polymer was 30 m
Since it is less than gKOH / g, both dispersion stability and storage stability are inferior.

[0123]

The aqueous ink compositions of the first to third aspects of the present invention contain a polymer or a complex containing an ultraviolet-absorbing functional group, so that the pigment or dye can be prevented from being deteriorated by ultraviolet rays. Moreover, these polymers and the like do not easily bleed out unlike ordinary ultraviolet absorbers, and thus the obtained printed matter can maintain excellent light fastness for a long period of time. Further, in the aqueous ink composition, when the base material is permeable such as paper, there is no problem that the ultraviolet absorber penetrates the base material and a sufficient effect of preventing deterioration cannot be obtained. . Further, in the aqueous ink compositions of the fourth to seventh inventions, since the pigment has a dispersing function by a polymer or a complex containing an ultraviolet absorbing functional group, it is possible to more reliably improve the light fastness of the printed matter. Can be. For this reason, printing inks such as gravure and flexo,
As an ink for writing implements, an ink for office automation equipment, and the like, the present invention can be applied to various printed materials such as paper, plastic molded products, films, glass, metals, and ceramics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09C 3/10 C09C 3/10 F term (Reference) 4J002 BC021 BD001 BF011 BG011 BG041 BG071 BG101 BG121 BJ001 BL011 CD191 CP031 FD096 4J037 AA02 AA22 AA25 CC14 CC17 CC28 CC29 DD04 DD05 EE03 EE28 EE43 FF15 FF22 4J039 AD02 AD04 AD08 AD10 AD11 AD12 AD13 AD15 AE11 BD02 BE01 BE02 BE24 CA06 EA35 FA01 FA02 FA04 FA06 GA03 GA09

Claims (7)

[Claims] 1. A polymer having an ultraviolet absorbing functional group,
An aqueous ink composition comprising at least one of a pigment and a dye. 2. The composite according to claim 1, wherein the polymer is a composite comprising an acrylic polymer and at least one of a polysiloxane polymer and a fluorine-containing polymer.
The aqueous ink composition as described in the above. 3. The aqueous ink composition according to claim 1, wherein the polymer is in the form of particles and has an average particle diameter of 0.001 to 0.9 μm. 4. An aqueous ink composition comprising a pigment coated with a polymer having an ultraviolet absorbing functional group. 5. The composite according to claim 4, wherein the polymer is an acrylic polymer and at least one of a polysiloxane polymer and a fluorine-containing polymer.
The aqueous ink composition as described in the above. 6. A polymer having a weight average molecular weight of 3,000.
The aqueous ink composition according to claim 4 or 5, which is the above. 7. An acrylic polymer having an acid value of 30 mg.
7. The method according to claim 4, which is at least KOH / g.
Item 10. The aqueous ink composition according to item 8.