JP2002249682A - Curing type coloring composition for ink jet recording and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing type coloring composition for ink jet recording which has an extremely good stability during its production process and whose coating film obtained by an ink jet method is highly practical due to the excel lence in transparency, heat resistance and chemical resistance, especially due to the excellent heat resistance, and to provide a color filter using the same. SOLUTION: The curing type coloring composition for ink jet recording uses a resin including carboxysilane group and epoxy group as a binder resin, and the color filter using the same is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable coloring composition and a color filter using the same. More specifically, paints, printing inks, colored filters using them, or color filters used for colored images formed on a substrate such as a color proof, for example, color liquid crystal displays, color scanners, solid-state imaging devices The present invention relates to a curable coloring composition suitable for applications requiring durability after a pattern forming step of an ink-jet method for a color filter used for a color filter and the like, and a color filter excellent in durability using the same.

[0002]

2. Description of the Related Art Conventionally, as one of curable coloring compositions using a coloring material such as a pigment or a dye, a photopolymerizable monomer or a photopolymerizable material is dispersed in or dissolved in a binder resin solution. A photocurable coloring composition in which a coloring material is dispersed or dissolved in a thermosetting resin or a thermosetting resin to which an initiator is added is known, and these are coated on a base material to form a colored pattern. There is known a colored image forming method in which a colored pattern is fixed by heat or light after the color pattern is formed. In particular, as one of the fields of application of these curable coloring compositions, there are color filters used in color liquid crystal displays, color scanners, solid-state imaging devices, and the like.

A color filter is provided on a transparent substrate provided with a light-shielding thin film called a black matrix so as to selectively transmit the three primary colors of red, green, and blue light, or cyan, magenta, and yellow, respectively. Are formed by arranging coloring materials in each pixel portion so as to selectively reflect the three primary colors.

As a method of forming this color filter,
Examples include a photolithography method, an electrodeposition method, a printing method, and an ink-jet method. Among these, the pigment dispersion type photolithography method, which is becoming mainstream, first forms a photosensitive resin layer in which a pigment is dispersed on a substrate, and then forms a monochromatic pattern by patterning it into a desired shape by a photolithography process. By repeating this process three times, pixels red, blue, green or cyan, magenta,
A color filter layer having three primary colors of yellow is formed. As a result, a high-precision pattern can be formed. However, since the same process is repeated three times, the cost increases, and the yield of the formed color filter decreases as the number of processes increases. In this method, the resin composition used must have photosensitivity.

On the other hand, the ink jet method capable of forming three primary colors as pixels in one step requires a small number of steps and is low in cost, and even if the resin composition used is photosensitive, There is an advantage that a thermosetting material having no property may be used.

As a binder resin used for a material for a color filter, an acrylic binder resin having excellent heat resistance and transparency is mainly used. Further, a functional group such as a carboxyl group is introduced for the purpose of improving the dispersibility of the coloring material and the physical properties of the coating film when the composition is cured.

However, the curable coloring composition used in the ink-jet method has difficulty in achieving both the stability during the manufacturing process and the physical properties of the cured coating film. However, there is a problem that it does not satisfy chemical resistance, high transparency and the like.

[0008]

The problem to be solved by the present invention is that the stability of the coloring composition during the production process is extremely good, and the coating film obtained by the ink jet method has excellent transparency and heat resistance. In particular, an object of the present invention is to provide a curable coloring composition for ink jet recording and a color filter using the same, which can provide a highly practical coating film having particularly excellent heat resistance.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a curable coloring composition for ink jet recording comprising a coloring material and a binder resin and the use of the same. In the color filter, by using a resin containing carboxysilane group and epoxy group as the binder resin, the stability during the manufacturing process is good, and the resulting coating film has excellent heat resistance, chemical resistance, and transparency. They found that a filter could be obtained, and completed the present invention.

That is, the present invention provides a curable coloring composition for ink-jet recording, comprising a resin (A) containing a carboxysilane group and an epoxy group and a coloring material (B). The present invention also provides a color filter using the obtained curable coloring composition for inkjet recording.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The resin (A) used in the present invention is not particularly limited as long as it contains a carboxysilane group and an epoxy group. For example, the resin (A) contains a carboxysilane group represented by the general formula (1) and an epoxy group. Compounds.

Embedded image (In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 1 to 18 carbon atoms, a phenyl group, an allyl group, or a hydrogen atom, and may be the same or different.)

The resin (A) is a copolymer obtained by polymerizing an ethylenically unsaturated monomer (a1) having a carboxysilane group and an ethylenically unsaturated monomer (a2) having an epoxy group. It is particularly preferred that there is.

As the ethylenically unsaturated monomer (a1) having a carboxysilane group, a vinyl monomer containing an ethylenically unsaturated group and a carboxylan group in one molecule can be used. Examples of the method include a method of reacting an ethylenically unsaturated monomer having a carboxyl group with a silane compound represented by the general formula (2) in the presence of a hydrochloric acid scavenger represented by triethylamine or pyridine. No.

[0014]

Embedded image (In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 1 to 18 carbon atoms, a phenyl group, an allyl group or a hydrogen atom, and may be the same or different.)

Examples of the ethylenically unsaturated monomer having a carboxyl group include ethylenically unsaturated mono- and di-carboxylic acids such as (meth) acrylic acid, coumaric acid, itaconic acid, maleic acid and fumaric acid; Monoalkyl maleate, monoalkyl fumarate,
Itaconic acid monoalkyl ester; hydroxyl group-containing monomers shown in [4] of other ethylenically unsaturated monomers (a3) described below, and acids such as phthalic anhydride, succinic anhydride, and trimellitic anhydride; And carboxyl group-containing ethylenically unsaturated monomers obtained by adding an anhydride.

Examples of the silane compound represented by the general formula (2) include trialkylchlorosilanes such as trimethylchlorosilane; dialkylchlorosilanes such as diethylchlorosilane; triphenylchlorosilane and triallylchlorosilane. .

The ethylenically unsaturated monomer (a1) having a carboxysilane group may be used alone or as a mixture of two or more.

The ethylenically unsaturated monomer (a2) having an epoxy group used in the present invention includes, for example, (meth)
Glycidyl acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-
Glycidyl butyl acrylate, (meth) acrylic acid-
It has an epoxy group such as 3,4-epoxybutyl, 4,5-epoxypentyl methacrylate, -6,7-epoxypentyl (meth) acrylate, -6,7-epoxypentyl α-ethylacrylate, etc. ) Acrylates; 3,4-epoxycyclohexylmethyl (meth) acrylate, lactone-modified (meth) acrylic acid-3,
Alicyclic epoxy monomers such as 4-epoxycyclohexylmethyl and vinylcyclohexene oxide;

Compound having two or more alicyclic epoxy groups in the molecule and compound having one polymerizable unsaturated double bond and one alicyclic epoxy group-reactive group in the molecule A glycidyl group-containing ethylenically unsaturated monomer obtained by reacting

A glycidyl group-containing ethylenically unsaturated monomer represented by the following formula (3):

Embedded image (However, R ₄ in the formula (3) represents a hydrogen atom or a methyl group, R ₅ represents an alkyl group having 1 to 5 carbon atoms, and m is a positive number of 1 to 6) Shall be.)

Specifically, for example, (meth) acrylates in which R ₄ is hydrogen or a methyl group, R ₅ is methyl, propyl, isopropyl, isobutyl, or amyl, and m is 1 to 3, etc. More specifically, for example, R ₄ is a methyl group, R ₅ is a methyl group, m =
And glycidylmethyl methacrylate.

Further, other ethylenically unsaturated monomers (a3) other than the ethylenically unsaturated monomer (a1) having a carboxysilane group and the ethylenically unsaturated monomer (a2) having an epoxy group Can be copolymerized.

Other ethylenically unsaturated monomers (a3) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ) Hexyl acrylate,
Heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate,
C1 such as stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate
(Meth) acrylates having an alkyl group of from 22 to 22;

Acrylic esters having an alicyclic alkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate; addition of tetrahydrofurfuryl alcohol and ε-caprolactone (Meth) acrylic acid ester;

Hydroxyethyl (meth) acrylate,
Acrylic esters having a hydroxyalkyl group such as hydroxypropyl (meth) acrylate and glycerol (meth) acrylate; lactone-modified hydroxyethyl (meth) acrylate;

Benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Acrylic acid ester having an aromatic ring;

(Meth) acrylates having a polyalkylene glycol group such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate;

Dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate;
Unsaturated dicarboxylic acid esters such as methyl ethyl itaconate;

Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene; butadiene, isoprene,
Diene compounds such as piperylene and dimethylbutadiene;
Vinyl halide and vinylidene halide such as vinyl chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride;

Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl cyanide such as acrylonitrile, methacrylonitrile and vinylidene cyanide; Acrylamide and its alkyd-substituted amides; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Silicon-containing (meth) acrylates and vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane and vinyltrimethoxysilane; trifluoroethyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, (Meth) acrylic acid having fluorine such as (per) fluoroalkyl (meth) acrylate having 1 to 18 carbon atoms in (per) fluoroalkyl group such as heptadecafluorodecyl acrylate or perfluoroethyloxyethyl (meth) acrylate Esters; dimethylaminoethyl methacrylate,
(Meth) acrylic acid esters having an amino group such as diethylaminoethyl methacrylate; (meth) acrylic acid esters having phosphorus represented by 2-methacryloyloxyethyl acid phosphate; and the like. The body (a3) may be used alone or in combination of two or more.

The resin (A) used in the present invention is, for example, an ethylenically unsaturated monomer (a) having a carboxysilane group.
1) and an ethylenically unsaturated monomer having an epoxy group (a
It can be obtained by copolymerizing 2) and, if necessary, another ethylenically unsaturated monomer (a3), and its copolymerization form is not particularly limited, but a radical polymerization initiator as a catalyst In the presence of, random copolymerization by addition polymerization,
Any of block copolymer, graft copolymer, etc. may be used,
As the copolymerization method, various polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used.

Solvents that can be used when using solution polymerization or the like include, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n- Amyl ketone, methyl-n-
Ketone solvents such as hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holone;

Ethyl ether, isopropyl ether,
ether solvents such as n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran;

Ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-
Ester solvents such as ethoxypropionate are exemplified.

The radical polymerization initiator as a catalyst includes:
Although various types can be used, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobis-
Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate,
Such as 1'-bis- (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, etc. Organic peroxides; hydrogen peroxide and the like. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

The molar ratio of the carboxysilane group of the ethylenically unsaturated monomer (a1) having a carboxysilane group to the epoxy group of the ethylenically unsaturated monomer (a2) having an epoxy group [(a1) / ( a2)] is preferably 0.2 / 1.0 to 5.0 / 1.0 from the viewpoint of excellent coating film performance.

The curable coloring composition for ink jet recording of the present invention contains a resin (A) and a coloring material (B), and examples of the coloring material (B) include dyes and pigments.

Various dyes can be used. For example, "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1970), "Color Material Engineering Handbook" (edited by the Color Material Association, Asakura Shoten, 1989) , "Technologies and Markets of Industrial Dyes" (CMC, 1983), "Chemical Handbook Applied Chemistry"
(Edited by The Chemical Society of Japan, Maruzen Shoten, 1986). More specifically, azo dyes,
Metal chain salt azo dye, pyrazolone azo dye, naphthoquinone dye, anthraquinone dye, phthalocyanine dye, carbonium dye, quinone imine dye, methine dye, cyanine dye, indigo dye, quinoline dye, nitro dye,
Examples include dyes such as xanthene dyes, thiazine dyes, azine dyes, oxazine dyes, and squarylium dyes.

As pigments, for example, commercially available pigments, or Color Index Handbook, “Latest Pigment Handbook, edited by the Japan Pigment Technical Association, 1977”, “Latest Pigment Application Technology” (CM
C Publishing, 1986), "Printing Ink Technology" (CMC
Publications, published in 1984) can be used. Specific examples thereof include inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, and carbon black, and anthraquinone pigments. , Perylene pigments, disazo pigments, phthalocyanine pigments, isoindoline pigments, dioxazine pigments, quinacridone pigments,
Organic pigments such as perinone pigments, triphenylmethane pigments, thioindigo pigments, diketopyrrolopyrrole pigments and the like can be mentioned, and these can be used alone or in combination. Of these, anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, dioxazine pigments, and carbon black are particularly preferred.

Specific examples of the pigment are shown below by color index (CI) numbers, but are not limited to these exemplified compounds. C. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123,
C. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I.
Pigment Red 216, C.I. I. Pigment Red 2
17, C.I. I. Pigment Red 220, C.I. I. Pigment Red 223, C.I. I. Pigment Red 22
4, C.I. I. Pigment Red 226, C.I. I. Pigment Red 227, C.I. I. Pigment Red 228,
C. I. Pigment Red 240, C.I. I. Pigment Red 254, C.I. I. Red pigments such as CI Pigment Red 48: 1;

C. I. Pigment Green 7, C.I. I.
Green pigments such as CI Pigment Green 36; I. Pigment Blue 15, C.I. I. Pigment Blue 15: 6,
C. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Blue pigments such as CI Pigment Blue 64; I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 30,
C. I. Pigment Violet 37, C.I. I. Pigment Violet 40, C.I. I. Violet pigments such as CI Pigment Violet 50;

C. I. Pigment Yellow 20, C.I.
I. Pigment Yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 86, C.I. I.
Pigment Yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I.
Pigment Yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I.
I. Pigment yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147,
C. I. Pigment yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 15
3, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 1
68, C.I. I. Yellow pigments such as CI Pigment Yellow 185; I. And black pigments such as CI Pigment Black 7, which can be used alone or in combination of two or more coloring materials.

Among these coloring materials (B), pigments are preferred from the viewpoint of excellent heat resistance and weather resistance.

The average particle size of the pigment is preferably in the range of 0.005 to 3 μm in order to obtain good coatability without generating thixotropy and to obtain transparency of the coating film. However, the thickness is particularly preferably 0.01 to 1 μm. In order to obtain such a particle size, a dispersion treatment such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint shaker, an attritor, a dispersion stirrer, and ultrasonic waves can be performed.

In preparing the curable coloring composition for ink jet recording in which the coloring material (B) is dispersed, a solvent (C) can be further added to the resin (A) and the coloring material (B). The solvent (C) preferably has a boiling point of 80 to 250 ° C., for example, aromatic solvents such as toluene, xylene and methoxybenzene; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Acetate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol, ethanol, propanol and ethylene glycol;
Ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether;
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline,
Nitrogen compound solvents such as pyridine; lactone solvents such as γ-butyrolactone; carbamates such as a 48:52 mixture of methyl carbamate and ethyl carbamate; these may be used alone or in combination. it can.

Further, a dispersant can be used in combination with the coloring material (B). The dispersant is not particularly limited, and various dispersants can be used. Examples thereof include surfactants, pigment intermediates, dye intermediates, polyester-based compounds, resin-based dispersions such as polyamide-based compounds and polyurethane-based compounds. Agents and the like. Commercial products of this resin type dispersant include:
For example, Dispervik 130, Dispervik 16
1, Dispervic 162, Dispervic 16
3, Dispervic 170, Fuka 46, Fuka 4
7, Solsperse 32550, Solsperse 2400
0, Addispar PB811, Azispar PB814 and the like. In addition, resin-type dispersants such as acryl-based and polyethylene-based resins can also be used.

The colorant (B) is preferably used in an amount of 10 to 70% by weight based on the solid content of the curable coloring composition. When a dispersant is used in combination, the dispersant is preferably used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the coloring material (B).

When the curable coloring composition for ink jet recording of the present invention is cured by light irradiation, it further contains a photocurable compound (D) and a photopolymerization initiator (E).

The photocurable compound (D) is a compound having a functional group capable of undergoing a polymerization or cross-linking reaction upon irradiation with ultraviolet light or visible light, and examples thereof include a radical polymerizable compound and a cationic polymerizable compound.

Specifically, for example, (meth) acrylic compounds, maleimide compounds, vinyl compounds, maleic esters, fumaric esters, crotonic esters, N-
Aromatic monomers such as vinylpyrrolidone, styrene derivatives and cinnamic acid esters; radical polymerization compounds such as N-vinylimidazole; and cationic polymerization compounds such as vinyl ether compounds, epoxy compounds and oxetane compounds. Among them, compounds having a radical polymerizable double bond in a molecule such as a (meth) acrylic compound are preferable.

Among the photocurable compounds (D), (meth) acrylic compounds include, for example, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropanedi (meth) acrylate, neomethylol Pentyl glycol di (meta)
Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyl) (Oxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate;

Phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A
Reaction products of epoxy resin such as epoxy resin and (meth) acrylic acid; polyols such as ethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethoxydiol of bisphenol A, polyester polyol, polybutadiene polyol, and polycarbonate polyol And organic polyisocyanates (e.g., tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and hydroxyl-containing (meth) acrylates (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( A reaction product of (meth) acrylate, 1,4-butanediol mono (meth) acrylate and the like);

The polybasic acid compound or its anhydride (for example,
Maleic acid, succinic acid, adipic acid, isophthalic acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and anhydrides thereof, and polyols (eg, ethylene glycol, propylene glycol, 3-methyl-1) , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, etc.) and a reaction product of polyester polyols and (meth) acrylic acid.

As the maleimide compound, a compound in which a maleimide group is bonded by an aliphatic group is preferable, and examples thereof include N-hexylmaleimide and N, N'-4,9-dioxa-1,12-bismaleimidododecane. Maleimide carboxylic acid (poly) alkylene glycol such as natural alkyl or alkyl ether maleimide, ethylene glycol bis (maleimide acetate), poly (tetramethylene glycol) bis (maleimide acetate), tetra (ethylene glycol-modified) pentaerythritol tetra (maleimide acetate) Ester, bis (2-
Carbonate maleimides such as (maleimidoethyl) carbonate; and urethane maleimides such as isophoronebisurethanebis (N-ethylmaleimide).

Examples of the vinyl compound include vinyl acetate, vinyl cinnamate, N-vinyl formaldehyde and the like.

As the vinyl ether compound, for example,
Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hydroxymethyl vinyl ether,
2-hydroxyethyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, diethylaminoethyl vinyl ether, cyclobutyl methyl vinyl ether, cyclopentyl vinyl ether, ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, 1,6-hexanediol methyl vinyl ether, and the like. .

Examples of the styrene derivative include styrene, divinylbenzene and the like.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N'-4,9 -Dioxa-1,12-bismaleimide dodecane, ethylene glycol bis (maleimide acetate), poly (tetramethylene glycol) bis (maleimide acetate), (ethylene glycol modified) pentaerythritol tetra (maleimide acetate), bis (2-maleimidoethyl) ) Carbonate, isophorone bis urethane bis (N-
Polyfunctional (meth) acrylates such as ethylmaleimide) and polyfunctional maleimides are particularly preferred because they cure well when irradiated with ultraviolet light, visible light, or the like.

The photocurable compound (D) may be used alone or as a mixture. The proportion of the photocurable compound (D) is not particularly limited, but does not impair the heat resistance and has excellent coating properties. To obtain a cured coating film, the resin (A) 100 of the present invention is used.
It is preferable to use 25 to 150 parts by weight based on parts by weight.

The photopolymerization initiator (E) is not particularly limited as long as it is a photopolymerization initiator that dissociates by light to generate a radical, and various types can be used. For example, benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone,
Benzophenones such as 4,4'-dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;
Xanthone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4
Xanthones such as dimethylthioxanthone and thioxanthone-4-sulfonic acid; thioxanthones;

Benzoin, benzoin methyl ether,
Acyloin ethers such as benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and benzoin butyl ether; α-diketones such as benzyl and diacetyl; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, p- Sulfides such as tolyl disulfide; 4-dimethylaminobenzoic acid, 4
-Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate,
2-dimethylhexyl 4-dimethylaminobenzoate, 4
Benzoic acids such as -dimethylaminobenzoic acid-2-isoamyl;

3,3'-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one,
2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-
Hydroxy-2-methylpropan-1-one;

1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2-diethoxyacetophenone, benzyldimethylketal, Benzyl-β-methoxyethyl acetal, 1-phenyl-
1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2-phenyl-1,2-butanedione-
2- (o-methoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarponyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, o −
Methyl benzoylbenzoate, bis (4-dimethylaminophenyl) ketone;

2,2'-bis (2-chlorophenyl)-
4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'
-Bis (2-bromophenyl) -4,4 ', 5,5'-
Tetrakis (4-ethoxycarbonylphenyl) -1,
2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4
-Dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5 ,
Biimidazoles such as 5'-tetraphenyl-1,2'-biimidazole;

P-dimethylaminoacetophenone, α,
α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2,4-bis-
Trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (4-ethoxy) phenyl-S-triazine, 2,4-bis-trichloro Methyl-
6- (3-bromo-4-ethoxy) phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone;

Anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, naphthalene Sulfonyl chloride, quinoline sulfonyl chloride,
n-phenylthioacridone, 4,4-azopisisobutyronitrile, diphenyldisulfide, benzthiazoldisulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin, Examples include a combination of a photoreducing dye such as methylene blue and a reducing agent such as ascorbic acid and triethanolamine.

The commercial names of the above-mentioned commercially available photopolymerization initiators include Irgacure-184, 149 and 26.
1, 369, 500, 651, 784, 81
9, 907, 1116, 1664, 1700,
1800, 1850, 2959, 4043, D
arocur-1173 (manufactured by Ciba Specialty Chemicals), Lucirin TPO (manufactured by BASF), KAY
ACURE-DETX, MBP, DMBI, EP
A, the same OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-1
0, 55 (manufactured by Stauffer Co. Ltd.), T
RIGONALP1 (AKZO Co. LTD), S
ANDORY 1000 (SANDOZ Co. LTD)
), DEAP (APJOHN Co. LTD), Q
UANTACURE-PDO, ITX, EPD (W
ARD BLEKINSOP Co. LTD).

Various photosensitizers can be used in combination with the photopolymerization initiator (E), for example, amines, ureas,
Examples thereof include a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile, and other nitrogen-containing compounds. These can be used alone or in combination of two or more.

The proportion of the photosensitizer to be used is not particularly limited. However, in order to suppress a decrease in sensitivity and to prevent precipitation of crystals and deterioration of physical properties of the coating film, the photosensitizer is used in the curable coloring composition. It is preferably used in an amount of 0.1 to 30% by weight, particularly preferably 1 to 20% by weight, based on the polymerization initiator (E).

The curable coloring composition for ink jet recording of the present invention can be obtained by mixing the above-mentioned components, and at this time, an appropriate solvent can be used. The solvent is not particularly limited as long as it does not react with the above components, and the solvent (C) used when preparing the coloring composition can be used alone or in combination of two or more.

The amount of the solvent used is such that the viscosity of the curable coloring composition is 50 mPa · s or less, especially 10 mPa · s, from the viewpoint of maintaining good dischargeability from the ink jet head.
s or less, and preferably in the range of 1 to 19 parts by weight per 1 part by weight of the total solids of the curable coloring composition.

The curable coloring composition for ink-jet recording of the present invention thus obtained is of a one-pack type and has excellent stability during the production process. Further, in a curing step after pixel formation, a cross-linked structure is generated by a cross-linking reaction of the polymer, and heat resistance and solvent resistance can be improved.

The curable coloring composition for ink-jet recording of the present invention may be further provided, if necessary, in a range which does not deviate from the object of the present invention, especially within a range capable of maintaining storage stability, heat resistance, solvent resistance and the like. Other components may be contained. Other components include, for example, various coupling agents (F); antioxidants; stabilizers; fillers; various leveling agents such as silicon-based, fluorine-based, and acrylic-based; A polycarboxylic acid or an anhydride thereof (G) for the purpose of curing; an epoxy compound (H) for the purpose of eliminating carboxyl groups remaining after curing by a reaction; and the like.

The coupling agent (F) is a compound that chemically bonds the inorganic material and the organic material to each other, or improves the affinity with a chemical reaction to enhance the function of the composite material. Compounds, titanium compounds, and aluminum compounds.

As the silane coupling agent, for example,
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane; γ-methacryloxypropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-uroidopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane; vinyltriacetoxysilane, vinyltrimethoxysilane; trimethoxysilylbenzoic acid; γ-isocyanatopropyl Examples thereof include triethoxysilane and the like, and oligomers and polymers made of these silane coupling agents and the like.

As the titanium coupling agent, for example,
Tetra-isopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium,
Titanium tetrastearoxy, di-isopropoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, dihydroxy
Bis (lactato) titanium, tetrakis (2-ethylhexanethiolat) titanium, tri-n-butoxytitanium monostearate, isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctyl pyrophosphate) titanate, tetra Isopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) Oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyltrioctanol titanate,
Isopropyl dimethacryl isosteroyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate,
Isopropyl tri (N-aminoethyl / aminoethyl)
Titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate and the like can be mentioned.

Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), and the like. Alkyl acetoacetate aluminum diisopropylate,
Aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetyl acetonate), cyclic aluminum oxide isopropylate and the like can be mentioned.

Among them, γ is particularly preferable in that it imparts particularly excellent smoothness, adhesion, water resistance and solvent resistance to various substrates.
-Glycidoxypropyltrimethoxysilane, β-
A silane coupling agent having an epoxy group such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, a silane coupling agent having an uroid group such as γ-uroidopropyltriethoxysilane, and the like are preferable. These coupling agents may be used alone or as a mixture.

The amount of the coupling agent added is such that the smoothness of the formed coating film, the adhesion to the substrate, the water resistance and the solvent resistance are kept good, the adhesion is improved, and the formed coating film is further added. In order to improve the energy ray curability of the resin (A), the amount is in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of the resin (A).

Examples of the polycarboxylic acid and its acid anhydride (G) include, for example, succinic acid, glutaric acid, adipic acid,
Aliphatic polycarboxylic acids such as butanetetracarboxylic acid, maleic acid and itaconic acid; hexahydrophthalic acid, 1,2
Alicyclic polycarboxylic acids such as -cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid and the like, and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid,
1,4,5,8-naphthalenetetracarboxylic acid, benzophenonetetracarboxylic acid;

Fatty acids such as phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, etc. Dicarboxylic anhydride; 1, 2,
Aliphatic polycarboxylic dianhydrides such as 3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride; Ester group-containing acid anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimetate;

Further, a resin having two or more carboxyl groups or an anhydride thereof in the molecule can be used, for example, a urethane resin having a carboxyl group, an acrylic resin, a polyester resin, a lactone-modified polyester resin, and a polyester amide. Resin, alkyd resin, polyether resin, modified polyether resin, polythioether resin, polycarbonate resin, polyacetal resin, polyolefin resin, epoxy modified resin, silicone resin,
A fluororesin; or an acid anhydride thereof.

A commercially available epoxy resin curing agent composed of a colorless carboxylic acid anhydride can also be used. For example, Adeka Hardener EH-700 [trade name (the same applies hereinafter) manufactured by Asahi Denka Kogyo Co., Ltd.], RIKACID-HH , MH-700
[Nippon Rika Co., Ltd.], Epikini 126, YH-3
06, DX-126 [Yukaka Epoxy Co., Ltd.]
And the like.

The above polycarboxylic acids and polycarboxylic anhydrides (G) can be used alone or in combination of two or more.

As the epoxy compound (H), for example,
Phenol / Novolak epoxy resin, Cresol /
Novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolak type epoxy resin, alicyclic epoxy resin, various glycols, alkylene oxide modified epoxy resin, glycidyl group-containing acrylic resin, alicyclic epoxy Group-containing acrylic resins and the like. These can be used alone or in combination of two or more.

A solution prepared by adjusting the curable coloring composition for ink jet recording of the present invention to an appropriate viscosity with a solvent is applied to the surface of a substrate such as a substrate on which a black matrix is formed by various ink jet techniques, for example, as an energy generating element. It is applied using a bubble jet (registered trademark) method using an electrothermal transducer, a piezo jet method using a piezoelectric element, or the like, to form a colored pattern.

The black matrix is formed by, for example, a method of forming a metal thin film by sputtering or vapor deposition and patterning by a photolithography process, a method of patterning by a photolithography process using a black resin composition, a method of forming by an ink jet method, and the like. It can be formed by various methods. At this time, depending on the properties of the curable coloring composition for inkjet recording, the black matrix may be subjected to a hydrophilic treatment, a hydrophobic treatment or an oil repellency treatment. Further, if necessary, the surface of the substrate can be treated with an adhesion aid such as the above-mentioned coupling agent (F) to improve the adhesion. Further, the substrate may be provided with an inkjet ink receiving layer.

The method for forming the color filter is not particularly limited. For example, after a colored pattern is formed on a substrate on which a black matrix is formed, heat curing and / or light curing are performed to form a pattern portion. There is a method in which the ink is cured, a protective film is formed if necessary, and a transparent conductive electrode such as ITO is formed.

Examples of the heat source used for thermosetting include a hot plate, an electric oven, an infrared heating furnace, and the like.
Various heating sources can be used. The heating temperature is preferably in the range of 100 to 300 ° C. in order to maintain good properties such as film strength, solvent resistance and alkali resistance, and also to prevent excessive volume shrinkage and maintain good adhesion and precision to the substrate. preferable.

The light source used for photocuring includes, for example, a light source from ultraviolet to visible light.
Light sources with a wavelength between 00 and 500 nm are preferred, and the use of ultraviolet light is particularly preferred for economic reasons. Examples of the light source include, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a chemical lamp,
Examples include a black light lamp, a mercury-xenon lamp, an excimer lamp, a short arc lamp, a helium / cadmium laser, an argon laser, and a THG or FHG light laser using a Nd-YAG laser.

The photocuring conditions are influenced by the type of light source used and the type and amount of the photoinitiator and cannot be unconditionally determined, but are preferably in the range of 100 to 3000 J / m ² from the viewpoint of productivity. When both photocuring and thermosetting are used, the above thermosetting conditions can be used.

The curable coloring composition for ink-jet recording of the present invention can be used for a color liquid crystal display, a color scanner,
It can be suitably used for a color filter used for a solid-state imaging device or the like.

The color filter selectively transmits the three primary colors of red, green, and blue light on a transparent substrate provided with a light-shielding thin film called a black matrix, or transmits cyan, cyan, and blue light, respectively.
It is formed by arranging a color material in each pixel portion so as to selectively reflect three primary colors of magenta and yellow.

The curable coloring composition for ink-jet recording of the present invention can be prepared by using the above-mentioned ink-jet method.
A plurality of different colors are simultaneously formed as a colored pattern on a substrate, and the three primary colors of red, green, and blue light or three colors of cyan, magenta, and yellow are formed by a simple process such as heat curing and / or light curing. It is possible to form each colored pixel such as a primary color and black used for light shielding, and to manufacture a color filter having excellent heat resistance, chemical resistance and the like.

[0096]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, all parts and percentages are by weight unless otherwise specified.

Synthesis Example 1 [Preparation 1 of ethylenically unsaturated monomer having carboxysilane group] n-hexane 320 was placed in a four flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet. 2.0 parts, 86.0 parts of methacrylic acid and 111.0 parts of triethylamine, and trimethylchlorosilane 12 was cooled with ice water.
0.0 parts was added dropwise while keeping the temperature at 30 ° C. or lower while paying attention to heat generation, and the reaction was continued at 30 ° C. for 1 hour. Thereafter, the triethylamine hydrochloride was filtered, and the filtrate was desolvated under reduced pressure to n.
After removing hexane, purification was carried out by distillation under reduced pressure to obtain an ethylenically unsaturated monomer having a carboxysilane group.
Hereinafter, this ethylenically unsaturated monomer is abbreviated as [a1-1].

Synthesis Example 2 [Preparation 2 of ethylenically unsaturated monomer having carboxysilane group] Using the same reactor as in Synthesis Example 1, n-hexane 30
3.0 parts, acrylic acid 72.0 parts, triethylamine 11
1.0 part was charged, and under cooling with ice water, 120.0 parts of trimethylchlorosilane was added dropwise while keeping the temperature at 30 ° C. or lower while paying attention to heat generation, and the reaction was continued at 30 ° C. for 1 hour. The subsequent treatment was performed in the same manner as in Synthesis Example 1 to obtain an ethylenically unsaturated monomer having a carboxysilane group. Hereinafter, this ethylenically unsaturated monomer is abbreviated as [a1-2].

Production Example 1 [Preparation 1 of Copolymer Containing Carboxysilane Group and Epoxy Group] In the same reactor as in Synthesis Example 1, propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc) 100.0 After heating the mixture to 60 ° C. while stirring, the ethylenically unsaturated monomer [a1-1] 2
7.0 parts, glycidyl methacrylate (hereinafter abbreviated as GMA) 30.0 parts, styrene (hereinafter abbreviated as St)
A mixed solution of 6.0 parts of 38.0 parts of 2,2′-azobis- (2,4-dimethylvaleronitrile) (hereinafter abbreviated as ABN-V) was added dropwise over 1 hour. After the dropwise addition, the mixture was maintained at 60 ° C for 1 hour, and then 0.08 parts of ABN-V was added.
Further, the reaction was carried out at the same temperature for 6 hours. Non-volatile content of the obtained resin solution (residual resin weight% after drying at 150 ° C for 1 hour)
Is 47.6%, the Gardner viscosity is PQ, and the acid value of the solution is 4 (the number of milligrams of potassium hydroxide required to neutralize the acid content in 1 g of the sample based on the prescribed method).
8. The number average molecular weight in terms of polystyrene was 11,000. Hereinafter, this copolymer is abbreviated as [A-1].

Production Example 2 [Preparation 2 of Copolymer Containing Carboxysilane Group and Epoxy Group] 100.0 parts of PGMAc were added to 100.0 parts of diethylene glycol dimethyl ether (hereinafter abbreviated as DMDG), and St3 was added to 32.5 parts of methyl glycidyl acrylate (hereinafter abbreviated as M-GMA).
Except having changed 8.0 parts to 35.5 parts and ABN-V6.0 parts to 9.0 parts, it carried out similarly to manufacture example 1, and the non-volatile content was 48.2% and the Gardner viscosity was F-. G, solution acid value is 4
8. A resin solution having a number average molecular weight of 5000 was obtained. Hereinafter, this copolymer is abbreviated as [A-2].

Production Example 3 [Preparation 3 of Copolymer Containing Carboxysilane Group and Epoxy Group] 30.0 parts of GMA was added to 40.8 parts of 3,4-epoxycyclohexyl methacrylate (hereinafter abbreviated as ECHMA). , St 38.0 parts were changed to 27.2 parts, and in the same manner as in Production Example 1, the nonvolatile content was 47.2%, the Gardner viscosity was JK, the solution acid value was 49, and the number average molecular weight was 10
000 resin solution was obtained. Hereinafter, this copolymer is referred to as [A-
3].

Production Example 4 [Preparation 4 of Copolymer Containing Carboxysilane Group and Epoxy Group] 27.0 parts of ethylenically unsaturated monomer [a1-1] was replaced with ethylenically unsaturated monomer [a1 -2] 24.6 parts, GMA
30.0 parts to 29.6 parts, St38.0 parts to 40.8 parts,
And except that ABN-V 6.0 was changed to 5.5,
In the same manner as in Production Example-1, a resin solution having a nonvolatile content of 47.7%, a Gardner viscosity of OP, a solution acid value of 48, and a number average molecular weight of 11,000 was obtained. Hereinafter, this copolymer is referred to as [A
-4].

Comparative Reference Production Example-1 [Preparation of Carboxyl Group-Containing Copolymer] 425.0 parts of PGMAc was charged into a four flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet. After heating to 90 ° C. while stirring, MAA4
2.8 parts, benzyl methacrylate (hereinafter abbreviated as BzMA) 286.1 parts, PGMAc 96.0 parts and t-
Butyl peroxy-2-ethylhexanate (hereinafter referred to as P-
16.5 parts) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was maintained at 90 ° C. for 2 hours, 1.7 parts of P—O was added, and the mixture was further reacted at the same temperature for 7 hours.
A resin solution having a solution acid value of 39 and a number average molecular weight of 9,500 was obtained. Hereinafter, this copolymer is abbreviated as [H-1].

Examples 1 to 5 and Comparative Example 1 Using a high-speed dispersing machine “TSG-6H” (manufactured by Igarashi Kikai Co., Ltd.) charged with zirconia beads of 0.5 mmφ,
The compositions shown in Table 1 (Formulation 1) and Table 1 (2) Formulation 1 were dispersed at a rotation speed of 30 s ^-1 for 8 hours to obtain a red pigment dispersion. Further, after adding and mixing the compositions shown in “Table 1 (1) Formulation 2” and “Table 1 (2) Formulation 2”, the mixture was filtered through a filter having a pore size of 1.0 μm to obtain a photocurable colorant for inkjet recording. A composition was obtained.

Example 6 and Comparative Example 2 Using a high-speed dispersing machine “TSG-6H” (manufactured by Igarashi Kikai Co., Ltd.) charged with zirconia beads of 0.5 mmφ,
The compositions shown in Table (1) Formulation 1 and Table 1 (2) Formulation 1 were dispersed at a rotation speed of 30 s ^-1 for 8 hours, and then filtered through a filter having a pore size of 1.0 μm to obtain an ink-jet ink. A photocurable coloring composition for recording was obtained.

[0106]

[Table 1]

[0107]

[Table 2]

<Footnotes to Tables (1) and (2)> All numbers in the tables represent parts by weight. PGMAc: propylene glycol monomethyl ether acetate DPHA: dipentaerythritol hexaacrylate PETA: pentaerythritol triacrylate Irg # 369: Irgacure # 369 Melamine resin: Super Beckamine J-820-60 (n, manufactured by Dainippon Ink and Chemicals, Inc.) -Butanol / xylene solution)

<Evaluation Method> Examples 1 to 5 and Comparative Example 1
Photocurable coloring composition for inkjet recording obtained in,
The thermosetting coloring composition for inkjet recording obtained in Example 6 and Comparative Example 2 was applied and cured by the following method,
An evaluation was performed. Table 2 shows the evaluation results.

(1) Photocuring method: The photocurable coloring composition for ink jet recording was applied using a piezo jet type head, and then preliminarily dried at 110 ° C. for 10 minutes to form a red patterned coating film. . The obtained coating film pattern was exposed to 1000 J / m ² using a high-pressure mercury lamp,
After baking was performed at 30 ° C. for 15 minutes.

(2) Thermosetting method: The thermosetting coloring composition for ink jet recording was applied using a piezo jet type head, and then preliminarily dried at 110 ° C. for 10 minutes to form a blue pattern coating film. . The obtained coating film pattern was cured in an oven at 200 ° C. for 30 minutes, and cured at 230 ° C.
For 15 minutes after baking.

(3) Heat resistance 1: A coating film applied and cured on a glass plate by an ink-jet method was heated at 280 ° C. for 30 minutes, and the change in the color tone (Y value) before and after heating was evaluated. . At this time, the difference ΔY in the change rate was less than 0.5, and the result was 0.5 or more. The chromaticity measurement was performed using an Olympus microspectrophotometer OSP-SP200.

(4) Heat resistance 2: A coating film applied and cured on a glass plate by an ink-jet method was heated at 280 ° C. for 30 minutes, and evaluated by a change in maximum light transmittance before and after heating. At this time, the rate of change was less than 5%, and the rate was 5% or more.

(5) Chemical resistance 1: Using a coating film applied and cured on a glass plate by an ink-jet method, the N.degree.
After immersion in -methyl-2-pyrrolidone for 30 minutes, the boundary surface of the liquid-immersed part was observed.

(6) Chemical resistance 2: A coating film applied and cured on a glass plate by an ink-jet method was coated with a rubbing tester (Taira Rika Kogyo Co., Ltd.) at 25 ° C.
Rubbing was performed with acetone under a load of 0 g, and the number of rubbings until reaching the glass substrate as the base was evaluated. At this time, the rubbing frequency of less than 25 times was evaluated as x, 25 or more and less than 100 times as ○, and 100 or more times as ◎.

[0116]

[Table 3]

When the absorption spectrum and the thin film X-ray diffraction of each coating film after the heat resistance test in Examples 1 to 6 were measured, no change in the crystal type and increase in the crystal diameter of the red or blue pigment was observed. When the absorption spectrum and the thin film X-ray diffraction of the coating film after the heat resistance test were measured in Comparative Example 1, it was confirmed that the crystal particles of the red pigment had increased.

In Comparative Example 2, since the dispersibility of the blue pigment was poor, the dischargeability was poor when applying using a piezo jet type head, and the head was clogged. Therefore, a blue pattern coating film could not be obtained, and evaluation could not be performed.

[0119]

The curable coloring composition for ink-jet recording of the present invention uses a resin containing a carboxysilane group and an epoxy group as a binder resin, and is excellent in pattern formation by an ink-jet method, and has transparency and heat resistance. In addition, it is possible to provide a curable coloring composition for ink jet recording having excellent chemical resistance and high practicality, and a color filter using the same.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H048 BA02 BA64 BB02 BB32 BB42 2H086 BA59 4J039 AE05 AE11 BA04 BA13 BA18 BA30 BA34 BA35 BA36 BA37 BC39 BC60 BE01 BE02 BE27 EA05 EA15 EA16 EA17 EA19 EA20 EA33 EA37 EA37 EA37 GA

Claims (4)

[Claims] 1. A curable coloring composition for ink-jet recording comprising a resin (A) containing a carboxysilane group and an epoxy group and a coloring material (B). 2. The resin (A) is obtained by polymerizing an ethylenically unsaturated monomer (a1) having a carboxysilane group and an ethylenically unsaturated monomer (a2) having an epoxy group as essential components. The curable coloring composition for inkjet recording according to claim 1, which is a copolymer comprising: 3. The curable coloring composition for inkjet recording according to claim 1, further comprising a photocurable compound (D) and a photopolymerization initiator (E). 4. A color filter using the curable coloring composition for inkjet recording according to claim 1. Description: