JP2001100413A - Photosensitive colored composition and color filter using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive colored composition excellent in heat, water, solvent and chemical resistances and having very good stability in steps and high practicality and to obtain a color filter using the composition. SOLUTION: The photosensitive colored composition contains a polymer having a carboxyl group and an epoxy group blocked with a protective group such as a cyclocarbonate group, a coloring material, a photopolymerizable monomer and a photopolymerization initiator as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive coloring composition and a color filter using the same. More specifically, paints, printing inks, colored display plates using them, or objects having a colored image formed on a substrate such as a color proof, particularly color liquid crystal displays, color scanners, and solid-state imaging devices. The present invention relates to a photosensitive coloring composition suitable for applications requiring durability after a pattern forming step by development, such as a filter, and a color filter having excellent durability using the same.

[0002]

2. Description of the Related Art Heretofore, as one of photosensitive coloring compositions using coloring materials such as pigments and dyes, photo-polymerization has been carried out on coloring compositions in which the coloring materials are dispersed using a binder resin and / or a dispersant. A photosensitive coloring composition to which a reactive monomer and a photopolymerization initiator are added is known. The composition is coated on a substrate, dried, exposed using a mask, developed and formed into a colored pattern, and then baked. A method of forming a colored image by a method such as fixing a pattern is known. In particular, as one of the fields of application of these photosensitive coloring compositions, there are color filters used for color liquid crystal displays, color scanners, solid-state imaging devices, and the like. The color filter is formed on a transparent substrate provided with a light-shielding thin film called a black matrix by arranging a color material in each pixel portion so as to selectively transmit the three primary colors of red, green, and blue, respectively. I have.

Many of the characteristics required for a material for a color filter are caused by a process for manufacturing a color liquid crystal display. For example, heat resistance required in a vapor deposition process and a firing process of a transparent electrode, a cleaning process and an alignment film coating process are required. Solvent resistance is required, and light resistance is also required because light transmitted through a color filter becomes image information during image display.

[0004] In order to satisfy these demands, pigments have been mainly used as coloring materials. As a production method, the “pigment dispersion method” has become mainstream (LCD panel member and material technology, pp. 23-25, Press Journal, March 20, 1999). As the binder resin used for this, an acrylic binder resin excellent in heat resistance, light resistance, transparency, and chemical resistance is mainly used.

[0005] Further, as a developer for development after exposure in a color filter manufacturing process by the "pigment dispersion method", an alkaline aqueous solution is preferred to an organic solvent in view of environmental problems. For this reason, in order to impart developability to an aqueous alkaline solution to the photosensitive coloring composition forming a color filter, the binder resin used at the time of dispersion of the pigment is required to have alkali solubility, and a binder resin having a carboxyl group is required. It is generally used as an alkali developing type photosensitive coloring composition. However, having a functional group such as a carboxyl group in the final use causes poor water resistance and chemical resistance.

[0006] Under such circumstances, a photosensitive coloring composition that achieves both good film properties such as good solvent resistance and heat resistance and alkali developability has been desired.

In recent years, various methods have been reported for satisfying the above-mentioned required characteristics and further improving the performance of the photosensitive coloring composition. For example, Japanese Patent Application Laid-Open No. 10-3167
As shown in JP-A-21, an alicyclic epoxy group is introduced into a binder resin and reacted with a carboxyl group to eventually consume unnecessary carboxylic acid. Further, a cross-linked structure generated by the reaction is introduced to improve the solvent resistance and the like. It has been proposed to improve heat resistance.

[0008] However, these colored photosensitive compositions certainly have good physical properties of a cured image portion, but have too high reactivity between an epoxy group and a carboxyl group, so that they can be produced as photosensitive colored compositions. There is a problem that the stability is insufficient on the surface and the storage surface, and as a result, the pattern developability is reduced.

[0009]

The problems to be solved by the present invention are, among others, excellent in heat resistance, water resistance, solvent resistance and chemical resistance, and the stability of the composition in the process is extremely good. An object of the present invention is to provide a photosensitive coloring composition having high practicality and a color filter using the same.

[0010]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks in the prior art, the present inventors have developed a photosensitive composition which is excellent in heat resistance, water resistance, solvent resistance and chemical resistance and has good stability. As a result of intensive trials and examinations for coloring compositions and color filters with excellent durability, the blocking of highly reactive epoxy groups reduces the reactivity at room temperature and at the temperature required during manufacturing. The inventors have found that the disadvantages of the technology can be solved, and have completed the present invention.

That is, [I] the present invention comprises, as main components, a polymer having an epoxy group and a carboxyl group blocked by a protecting group, a coloring material, a photopolymerizable monomer, and a photopolymerization initiator. The present invention also provides a photosensitive colored composition, and [II] the present invention provides a photosensitive colored composition in which an epoxy group blocked by a protecting group is 2-oxo-1,3-dioxolane-
The present invention provides a photosensitive colored composition according to the above [I], which is a 4-yl group. [III] The present invention uses the photosensitive colored composition according to the above [I] and [II]. The purpose of the present invention is to provide a color filter.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

An example of an epoxy group blocked by a protecting group in a polymer having an epoxy group and a carboxyl group blocked by the protecting group of the present invention is, for example, 2-oxo-1,3-dioxolan-4-yl. (Hereinafter, referred to as a cyclocarbonate group). Hereinafter, a cyclocarbonate group will be described as a blocked epoxy group.

The cyclocarbonate group in the polymer as the binder resin of the present invention is represented by the following general formula:

[0015]

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(Where R in the formula is
1, R2 and R3 may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

Here, the polymer of the present invention, 2-
A polymer having an oxo-1,3-dioxolan-4-yl group and a carboxyl group (hereinafter, referred to as a cyclocarbonate polymer) refers to, for example, at least one ethylenically unsaturated double bond and one It may be obtained by a copolymerization reaction of a monomer having two or more cyclocarbonate groups with another polymerizable unsaturated monomer, or may be a known and commonly used isocyanate such as an isocyanateethyl (meth) acrylate copolymer. It may be obtained by adding a carbonate monoalcohol to a group-containing polymer, or may be obtained by adding a carbonate monoalcohol to a known and commonly used acid chloride-containing polymer. Among these, a monomer having both an ethylenically unsaturated double bond and a cyclocarbonate group (hereinafter, referred to as a monomer)
By a copolymerization reaction of a cyclocarbonate monomer) with another polymerizable unsaturated monomer, it is preferably used because it is simple.

As a typical example of the cyclocarbonate monomer, the following general formula can be used.

[0019]

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(Wherein R in the formula represents a hydrogen atom or a methyl group, and R1, R2 and R3 may be the same or different and each represents a hydrogen atom or a C1-4 And n represents 1 to 6
Which is a positive number).

Specifically, 2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl (meth) acrylate, 3,4-carbonatebutyl (meth) acrylate, 3-methyl-3 ,
4-carbonate butyl (meth) acrylate, 4-methyl-3,4-carbonate butyl (meth) acrylate, 3-methyl-3,4-carbonate butyl (meth)
Acrylate, 6,7-carbonate hexyl (meth)
(Meth) acrylates such as acrylate, 5-ethyl-5,6-carbonate hexyl (meth) acrylate and 7,8-carbonate octyl (meth) acrylate; 2,3-carbonate propyl vinyl ether, methyl-2,3-carbonate Compounds such as propyl malate, or methyl-2,3-carbonate propyl crotonate. These cyclocarbonate monomers may be used alone or in combination of two or more.

The cyclocarbonate polymer is preferably a polymer further containing a carboxyl group in order to provide the photosensitive coloring composition of the present invention with a function as an alkali developing type pattern forming material. A polymer having a cyclocarbonate group and a carboxyl group can be obtained by polymerizing an ethylenically unsaturated monomer having a carboxyl group as an ethylenically unsaturated monomer copolymerizable with a cyclocarbonate monomer. . Examples of the ethylenically unsaturated monomer having a carboxyl group include ethylenically unsaturated mono- and di-carboxylic acids such as acrylic acid, methacrylic acid, coumaric acid, itaconic acid, maleic acid and fumaric acid; A monoalkyl ester, a monoalkyl fumarate or a monoalkyl itaconate; or a hydroxyl group-containing monomer represented by (4) among the ethylenically unsaturated monomers copolymerizable with a cyclocarbonate monomer described below. An ethylenically unsaturated monomer having a carboxyl group obtained by adding an acid anhydride such as phthalic anhydride, succinic anhydride or trimellitic anhydride to the monomer.

In the polymer as the binder resin of the present invention, by blocking the epoxy group with a protecting group, the reactivity of the epoxy group is suppressed at room temperature and at the temperature exposed in the process, so that the pattern forming step by development can be performed. Stability before passing can be increased, and furthermore, in a baking step performed after the pattern forming step, it reacts with a carboxyl group coexisting in the polymer to eventually consume unnecessary carboxylic acid, and further the reaction The resulting crosslinked structure can be introduced to improve solvent resistance and heat resistance. That is, the epoxy group is protected in order to impart optimum stability to the photosensitive coloring composition by the process temperature difference between the exposure / development step and the color pattern baking step.

The above-mentioned cyclocarbonate monomer and the ethylenically unsaturated monomer having a carboxyl group can be used after being copolymerized with another copolymerizable ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer of the present invention include: (1) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate,
Alkyl groups having 1 to 22 carbon atoms such as hepsyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, stearyl acrylate, octadecyl acrylate, docosyl acrylate, etc. (2) alicyclic alkyl such as cyclohexyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxy acrylate, etc. Acrylate having a group, or methacrylate having an alicyclic alkyl group similar to the above, or acrylate or methacrylic acid of tetrahydrofurfuryl alcohol and ε-caprolactone adduct (3) acrylates having an aromatic ring such as benzoyloxyethyl acrylate, benzyl acrylate, phenylethyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and 2-hydroxy-3-phenoxypropyl acrylate; Or methacrylic ester having the same aromatic ring as described above, etc. (4) Acrylic ester having a hydroxyalkyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate, glycerol acrylate, or methacryl having the same hydroxyalkyl group as described above Acid ester or lactone-modified hydroxyethyl acrylate or hydroxyethyl methacrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, etc. (5) Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, α-n-propyl acryl Glycidyl acid, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, methacrylic acid-4,
5-epoxypentyl, acrylic acid-6,7-epoxypentyl, methacrylic acid-6,7-epoxypentyl,
α-ethylacrylic acid-6,7-epoxypentyl and the like;
Fats such as 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, lactone-modified 3,4-epoxycyclohexyl acrylate, lactone-modified 3,4-epoxycyclohexyl methacrylate, and vinylcyclohexene oxide A cyclic epoxy monomer and a compound having two or more alicyclic epoxy groups in the molecule and a group having one polymerizable unsaturated double bond and one alicyclic epoxy group in the molecule; A glycidyl group-containing ethylenically unsaturated monomer obtained by reacting with a compound having the following general formula:

[0025]

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(Wherein, R4 in the formula represents a hydrogen atom or a methyl group, R5 represents an alkyl group having 1 to 5 carbon atoms, and m is a positive number of 1 to 6) A) a glycidyl group-containing ethylenically unsaturated monomer represented by the formula: for example, R4 is hydrogen or a methyl group;
An acrylate or methacrylate in which the lower alkyl group of R5 is methyl, propyl, isopropyl, isobutyl, amyl or the like; (6) dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate,
Unsaturated dicarboxylic acid esters such as methyl ethyl fumarate, methyl butyl fumarate and methyl ethyl itaconate (7) Styrene derivatives such as styrene, α-methyl styrene and chlorostyrene (8) Diene such as butadiene, isoprene, piperylene and dimethyl butadiene (9) Vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides (10) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone (11) Vinyl esters such as vinyl acetate and vinyl butyrate (12) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether; (13) vinyl cyanide such as acrylonitrile, methacrylonitrile, and vinylidene cyanide; (14) acrylamide and its alkyd-substituted amide; (15) N-phenylmale N-substituted maleimide such as N-cyclohexylmaleimide (16) Fluorine-containing α- such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene Olefins; or (per) fluoroalkyl perfluorovinyl ethers having 1 to 18 carbon atoms in a (per) fluoroalkyl group such as trifluoromethyltrifluorovinylether, pentafluoroethyltrifluorovinylether or heptafluoropropyltrifluorovinylether 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5
H-octafluoropentyl (meth) acrylate, 1
(Per) fluoroalkyl (meth) having 1 to 18 carbon atoms in a (per) fluoroalkyl group such as H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Fluorine-containing ethylenically unsaturated monomers such as acrylates (17) silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane (18) N, N-dimethylaminoethyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylates such as N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate are exemplified.

These ethylenically unsaturated monomers copolymerizable with the cyclocarbonate monomer can be used alone or in combination of two or more compounds.

The cyclocarbonate polymer of the present invention as described above can be obtained by copolymerizing a cyclocarbonate monomer and another copolymerizable ethylenically unsaturated monomer. Although not limited, any of random copolymers, block copolymers, graft copolymers, etc. by addition polymerization in the presence of a catalyst (polymerization initiator) may be used, and the copolymerization method is a bulk polymerization method or a solution polymerization method. Known polymerization methods such as a suspension polymerization method and an emulsion polymerization method can be used.

Here, typical solvents that can be used for solution polymerization and the like include, for example, (1) acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n
-Butyl ketone, methyl isobutyl ketone, methyl-n
-Ketone solvents such as amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holone (2) ethyl ether, isopropyl ether, n-butyl ether; Ether solvents such as diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, and tetrahydrofuran (3) 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-ethoxypropionate, etc. Ester solvents. Further, as a radical polymerization initiator as a catalyst,
Generally known ones can be used, and typical ones include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile) , 2,2'-azobis- (4-methoxy-
Azo compounds such as 2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-
Butyl peroxypivalate, 1,1'-bis- (t-
Organic peroxides such as butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, and t-hexylperoxy-2-ethylhexanoate; and hydrogen peroxide. 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 amount of the cyclocarbonate monomer used is 1 to 50% by weight, preferably 2 to 40% by weight, based on the total amount of the monomer and the copolymerizable ethylenically unsaturated monomer. It is. If the amount is less than 1% by weight, the effect of the compound cannot be expected. If the amount exceeds 50% by weight, the choice of the solvent to be used is unpreferably reduced.

The cyclocarbonate polymer of the present invention is preferably a polymer having an ethylenically unsaturated double bond in the molecule. In this polymer, an ethylenically unsaturated dipolymer bond can be further introduced into a side chain of the cyclocarbonate polymer by reacting the cyclocarbonate polymer with an ethylenically unsaturated monomer. By introducing an ethylenically unsaturated dipolymer bond into the side chain of the cyclocarbonate polymer of the present invention, the compound itself can be provided with energy ray curability, and at least two ethylenically By combining with a photopolymerizable monomer having an unsaturated double bond, a cyclocarbonate polymer and at least 2
A cross-linking reaction can be carried out with a single photopolymerizable monomer having an ethylenically unsaturated double bond, and a coating film having excellent durability can be obtained.

Since the cyclocarbonate polymer of the present invention has both a cyclocarbonate group and a carboxyl group, the photosensitive coloring composition of the present invention can be prepared by a known method, for example, through a pattern exposure step and a development step.
A coating film having a predetermined pattern can be easily formed. That is, when the photosensitive coloring composition of the present invention is immersed in an aqueous alkali solution such as sodium carbonate or sodium hydroxide, the carboxyl groups in the cyclocarbonate polymer are neutralized and solubilized by the aqueous alkali solution. is there.

Here, the acid value of the cyclocarbonate polymer having a carboxyl group (the number of milligrams of potassium hydroxide required to neutralize the acid content present in 1 g of the sample based on a prescribed method) is as follows: It is not particularly limited as long as it can be developed with an aqueous alkali solution type developer selected according to the purpose, but is preferably used in the range of 20 to 250 mgKOH / g.

Further, the cyclocarbonate polymer in the present invention is preferably a polymer having a hydroxyl group together with a carboxyl group. This polymer can be obtained by copolymerizing a hydroxyl group-containing ethylenically unsaturated monomer with at least one carboxyl group-containing ethylenically unsaturated monomer in the molecule. By copolymerizing the hydroxyl group-containing monomer, solubility in an alkaline aqueous solution is improved, and the photosensitive coloring composition containing the cyclocarbonate polymer has no development residue at the time of development,
It is possible to easily obtain a coating film on which a sharp pattern is formed.

The molecular weight of the cyclocarbonate polymer obtained by the above-mentioned method is usually determined by polystyrene in order to form a uniform coating film on the substrate using the energy-curable resin composition of the present invention and to impart various coating film properties. It is desirable that the reduced number average molecular weight exceeds 2,000. If the number average molecular weight is less than 2,000, a coating film performance which is expected cannot be obtained sufficiently. When the molecular weight further increases and the number average molecular weight becomes 100,000 or more, the viscosity of the resin increases, and depending on the coating method, the coating workability or the like tends to deteriorate. What is necessary is just to select suitably according to the purpose of use, coating film performance, and selection of a coating method.

Next, the photosensitive coloring composition of the present invention contains a coloring material such as a dye or a pigment in addition to the above-mentioned cyclocarbonate polymer. Among these, pigments are preferably used in terms of heat resistance and light resistance.

As the organic pigment used in the present invention, for example, CI Pigment Red 9, CI Pigment Red 9
7, CI Pigment Red 122, CI Pigment Red 12
3, CI Pigment Red 149, CI Pigment Red 16
8, CI Pigment Red 177, CI Pigment Red 18
0, CI Pigment Red 192, CI Pigment Red 21
5, CI Pigment Red 216, CI Pigment Red 217, C.
I. Pigment Red 220, CI Pigment Red 223, CI
Red pigments such as CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 227, CI Pigment Red 228, CI Pigment Red 240, CI Pigment Red 254, and CI Pigment Red 48: 1; CI Pigment Green 7,
Green pigments such as CI Pigment Green 36; blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 30, CI
Violet pigments such as CI Pigment Violet 37, CI Pigment Violet 40, CI Pigment Violet 50; CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 125,
CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI
Pigment Yellow 154, CI Pigment Yellow 166,
CI Pigment Yellow 168, CI Pigment Yellow 1
Yellow pigments such as 85; black pigments such as CI Pigment Black 7; Examples of the inorganic dye used in the present invention include carbon, titanium, barium, aluminum, calcium, iron, lead, and cobalt.

These coloring materials can be used alone or in combination of two or more.

Usually, when preparing a coloring composition in which a coloring material is dispersed, the coloring composition is prepared by combining a solvent with at least the coloring material and the binder resin. Solvents that can be used when preparing the coloring composition in which the coloring material is dispersed are not particularly limited, but examples thereof include aromatic solvents such as toluene, xylene, and methoxybenzene, and ethyl acetate and butyl acetate. Acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol and ethanol; butyl cellosolve; propylene glycol monomethyl ether; diethylene glycol ethyl ether , Ether solvents such as diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, aliphatic hydrocarbon solvents such as hexane,
N, N-dimethylformamide, γ-butyrolactam,
Nitrogen compound solvents such as N-methyl-2-pyrrolidone, aniline and pyridine; lactone solvents such as γ-butyrolactone; methyl carbamate and ethyl carbamate;
8:52, such as a mixture of carbamates, water, and the like.

Further, a dispersant can be used when a coloring material is dispersed to prepare a coloring composition. Here, the dispersant that can be used in dispersing the colorant is not particularly limited, but examples thereof include a surfactant, an intermediate of a pigment, an intermediate of a dye, and a polyamide-based compound or a polyurethane-based compound. Such a resin-type dispersant can be used. As commercial products of this resin-type dispersant, for example, Dispervic 130, Dispervic 161, Dispervic 162, Dispervic 163, Dispervic 170, Ffka 46, Ffka 47, Solsperse, and the like can also be used. In addition, resin-based dispersants such as acryl-based and polyethylene-based resins can also be used.

Further, examples of the dispersing machine that can be used for preparing the coloring composition by dispersing the coloring material include a roll mill, a ball mill, a bead mill, an attritor, and a dispersion stirrer.

The photosensitive coloring composition of the present invention comprises, together with the above-mentioned cyclocarbonate polymer and coloring material, a photopolymerizable monomer having at least two ethylenically unsaturated double bonds in the molecule (hereinafter referred to as photopolymerizable monomer). And a photopolymerization initiator.

Examples of the photopolymerizable monomer of the present invention include trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Acrylate, pentaerythritol tri (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, epoxy (meth) acrylate For example, urethane (meth) acrylates, such as ethylene glycol, polyethylene glycol, and the like, such as a reaction product of an epoxy resin such as a phenol novolak epoxy resin, a cresol novolak epoxy resin, a bisphenol A epoxy resin, and (meth) acrylic acid. , Polypropylene glycol, polytetramethylene glycol, bisphenol A
Polyols such as polyethoxydiol, polyester polyol, polybutadiene polyol, and polycarbonate polyol; organic polyisocyanates (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and hydroxyl group-containing (meth) acrylates ( For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
1,4-butanediol mono (meth) acrylate, etc.), polyester (meth) acrylates, such as polybasic acid compounds or anhydrides thereof (eg, 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.

Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are known from the viewpoint of active energy ray curing sensitivity. Is particularly preferred.

These may be used alone or as a mixture, and the use ratio is not particularly limited, but it is preferable to use 25 to 150% by weight of the binder resin. If it exceeds 150% by weight, the alkali solubility which is the object of the present invention also decreases, while if it is less than 25% by weight, it becomes difficult to obtain a cured coating film having desired coating film properties, and it becomes difficult to form a pattern. Not preferred.

As the photopolymerization initiator of the present invention, a photopolymerization initiator capable of dissociating by light to generate a radical can be used, and a known photopolymerization initiator can be used. Representative examples of the photopolymerization initiator used in the present invention include: (1) benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4 ' Benzophenones such as -bisdiethylaminobenzophenone, 4,4-dichlorobenzophenone, Michler's ketone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (2) xanthones, thioxanthones, 2-methylthioxanthones, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone,
2,4-dimethylthioxanthone, thioxanthone-4-
Xanthones such as sulfonic acid, thioxanthones (3) acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether; (4) benzyl, diacetyl Α-diketones such as (5) Sulfides such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide and p-tolyl disulfide (6) 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylamino Benzoic acids such as ethyl benzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, In addition, 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-propane-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-methoxyethylacetal, 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, -Phenyl-3-ethoxy-propanetrione-2- (o-
Benzoyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-
Dimethylaminoacetophenone, α, α-dichloro-4
-Phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2- (o-chlorophenyl)-
4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2,4-
Bis-trichloromethyl-6- (4-ethoxy) phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazineanthraquinone, 2-t-butyl Anthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibensuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-pis (p-azidobenzylidene) cyclohexane, 2,6-pis (p-azido Benzylidene)
-4-Methylcyclohexanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azopisisobutyronitrile, diphenyldisulfide, benzthiazoldisulfide, triphenylphosphine, carbon tetrabromide And a combination of a photoreducing dye such as tribromophenylsulfone, benzoin peroxide, eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine.

As the photopolymerization initiator, Irgacure-1
84, 149, 261, 369, 500, 6
51, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2
959, 4043, Darocur-1173 (manufactured by Ciba Specialty Chemicals), Lucirin TPO (manufactured by BASF), KAYACURE-DETX, MBP, DMBI, EPA, OA
(Manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (STAUFFE
R Co.LTD), TRIGONALP1 (AKZO Co.LTD), SANDO
RY 1000 (made by SANDOZ Co.LTD), DEAP (APJOHN Co.LTD)
QUANTACURE-PDO, ITX, EPD (WARD BLEKINSOP)
Co., Ltd.) and the like.

A known and commonly used photosensitizer can be used in combination with such a photopolymerization initiator. Illustrative examples of the photosensitizer used in the present invention include amines,
Examples include ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles and other nitrogen-containing compounds.

These can be used alone or in combination of two or more. The amount used is not particularly limited, but is preferably used so as to contain 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the photopolymerizable monomer in the composition. If it is less than 0.1% by weight, the sensitivity is lowered, and if it exceeds 30% by weight, crystals are precipitated, and the properties of the coating film are deteriorated.

The photosensitive coloring composition of the present invention can be obtained by mixing the above various components. As a method of mixing these components, a method of mixing these components with an appropriate solvent can be used. The solvent in this method is not particularly limited as long as it does not react with each of the above-mentioned components, and various solvents can be used, and various solvents shown when polymerizing the above-mentioned cyclocarbonate polymer are used. Various solvents and the like described when dispersing the solvent and the coloring material can be used. These can be used alone or
A combination of more than one species can also be used. in this case,
All components may be adjusted with the same solvent, or, if necessary, each component may be prepared with different solvents to form two or more solutions,
These solutions may be mixed to prepare a solution of the active energy ray-curable composition of the present invention.

The photosensitive coloring composition of the present invention thus obtained is excellent in storage stability in one liquid, and further uses a cyclocarbonate polymer having a carboxyl group. In order to improve the water resistance, chemical resistance, etc. caused by the reaction, the carboxyl group is consumed by the reaction of the cyclocarbonate group and the carboxyl group, and the heat resistance and solvent resistance are improved by the generation of the crosslinked structure generated by the reaction it can. Further, a composition of a cyclocarbonate polymer having a carboxyl group in an unexposed state is easily dissolved in an alkali developing solution, so that a pattern can be formed.

The photosensitive coloring composition of the present invention may further contain, if necessary, other components within a range that does not deviate from the object of the present invention, in particular, a range in which storage stability, heat resistance, solvent resistance and the like can be maintained. May be contained. Such other components include known and commonly used curing catalysts, coupling agents and antioxidants, stabilizers, fillers, silicon-based, fluorine-based, acrylic-based leveling agents, polyvalent carboxylic acids and anhydrides thereof. And epoxy compounds can be added.

Examples of the ring opening catalyst used in the present invention include a ring opening catalyst for a cyclocarbonate group and a ring opening catalyst for an epoxy group. Of these various ring-opening catalysts, particularly only representative ones are exemplified, tetramethylammonium bromide, trimethylbenzylammonium hydroxide, 2-hydroxypyridine, trimethylbenzylammonium methoxide, phenyltrimethylammonium chloride, Phenyltrimethylammonium bromide, phenyltrimethylammonium hydroxide, phenyltrimethylammonium iodide, phosphocholine chloride sodium salt, stearylammonium bromide, tetra-n-
Amyl ammonium iodide, tetra-n-butylammonium bromide, tetra-n-methylammonium hydroxide, tetra-n-butylammonium phosphate, tetra-n-decylammonium trichloride, tetraethylammonium hydroxide, tetraethylammonium tetrafluoroborate, Quaternary ammonium such as acetylcholine bromide, alkyl dimethyl pendant ammonium chloride, pendyl choline bromide, pendyl-n-butylammonium bromide, betaine, butyryl chloride, bis (tetra-n-butylammonium) dichromate or trimethylvinylammonium bromide Salts: allyltriphenylphosphonium chloride, n-
Amyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, bromomethyltriphenylphosphonium bromide, 2-dimethylaminoethyltriphenylphosphonium bromide, ethoxycarbonylphosphonium bromide, n-heptyltriphenylphosphonium mubromide, methyltriphenylphosphonium bromide, Phosphonium salts such as tetrakis [hydroxymethyl] phosphonium sulfate or tetraphenylphosphonium bromide;
Acid catalysts such as phosphoric acid, p-toluenesulfonic acid or dimethyl sulfate; or carbonates such as calcium carbonate. These can be used alone or in combination of two or more.

The amount of the ring-opening catalyst is not particularly limited, but is preferably used such that it is contained in an amount of 0.01 to 5% by weight based on the cyclocarbonate polymer in the composition. 0.
If the content is less than 01% by weight, no effect is exhibited, and conversely, 5% by weight
It is not preferable that the amount is too large beyond the range, because physical properties such as a decrease in water resistance of the coating film are caused.

The coupling agent used in the present invention is
Inorganic materials and organic materials are chemically defined as compounds that combine the two or improve the affinity with a chemical reaction to enhance the function of the composite material.A typical coupling agent is silane. Compounds, titanium compounds, and aluminum compounds. Typical examples of the silane coupling agents are (1) γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropylmethyl. Dimethoxysilane, (2) γ-methacryloxypropyltrimethoxysilane, (3) γ-glycidoxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (4) γ-mercaptopropyltrimethoxysilane (5) vinyltriacetoxysilane, vinyltrimethoxysilane, (6) trimethoxysilylbenzoic acid (7) γ -Isocyanatopropyltriethoxysilane and the like, and oligomers and polymers composed of these silane coupling agents and the like.

As the titanium coupling agent, tetra-
i-propoxytitanium, tetra-n-butoxytitanium,
Tetrakis (2-ethylhexoxy) titanium, tetrastearoxytitanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminato) titanium, dihydroxybis (lactato) titanium, Tetrakis (2-ethylhexanediolato) titanium, tri-n-butoxytitanium monostearate, isopropyltriisostearoyl titanate,
Isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-
Diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanolol titanate, isopropyldimethacrylisostearoyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate, and the like. Can be.

As the aluminum coupling agent, aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum s
ec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetonate) And cyclic aluminum oxide isopropylate.

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 is preferable. These coupling agents can be used alone or in combination of two or more.

The compounding amount of the coupling agent in the resin composition of the present invention depends on the amount of the cyclocarbonate polymer 100
It is in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight per part by weight. If the amount of the coupling agent is less than 0.1 part by weight, the smoothness of the formed coating film and the adhesion, water resistance and solvent resistance to the substrate are insufficient. In addition to improving the curability, the curability of the formed coating film is undesirably reduced.

Further, the photosensitive coloring composition of the present invention may contain an epoxy compound, a polycarboxylic acid and an anhydride thereof. Typical examples of the above-mentioned polyvalent carboxylic acids and their acid anhydrides include: (1) aliphatic polyvalent acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; Carboxylic acid (2) Alicyclic polycarboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid and the like, and phthalic acid, isophthalic acid, terephthalic acid Acid, trimellitic acid, pyromellitic acid, 1,4,5,8-
Examples include naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid.

The following are typical examples of polycarboxylic anhydrides: (1) phthalic anhydride, itaconic anhydride, succinic anhydride,
Fatty acid dicarboxylic anhydrides such as citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hymic anhydride (2) 1,2,3,4- Aliphatic polycarboxylic dianhydrides such as butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride (3) pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride (4) Ester anhydrides containing ester groups such as ethylene glycol bistrimellitate and glycerin tristrimetate can be mentioned. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent composed of a colorless acid anhydride can also be suitably used. Specific examples include Adeka Hardener EH-700 [trade name (the same applies hereinafter) manufactured by Asahi Denka Kogyo Co., Ltd.], RIKACID-HH and MH-700.
[Nippon Rika Co., Ltd.], Epikini 126, YH-30
And DX-126 [manufactured by Yuka Shell Epoxy Co., Ltd.].

Further, as the one or more compounds selected from the group consisting of polyvalent carboxylic acids and their anhydrides, resins having two or more carboxyl groups or their anhydrides in the molecule may be used. Can also be used. Among them, particularly typical ones, for example, having a carboxyl group, urethane resin, acrylic resin, polyester resin, lactone-modified polyester resin, polyesteramide resin, alkyd resin, polyether resin, modified polyether resin, Examples thereof include a polythioether resin, a polycarbonate resin, a polyacetal resin, a polyolefin resin, an epoxy-modified resin, a silicone resin, and a fluororesin.

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

Further, the above-mentioned epoxy compounds include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A novolak epoxy resin, alicyclic epoxy resin Resins, various glycols, alkylene oxide-modified epoxy resins, glycidyl group-containing acrylic resins, alicyclic epoxy group-containing acrylic resins, and the like can be used alone or in combination of two or more.

A desired coating film can be obtained by applying the photosensitive coloring composition of the present invention prepared as described above to the surface of a substrate, performing a patterning treatment, and curing by heating.

The method of applying the solution of the photosensitive coloring composition of the present invention to the surface of a substrate is not particularly limited, and various methods such as a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and the like can be used. One of the features of the present invention is that the photosensitive coloring composition of the present invention is suitable for a spin coating method.

An example of a method of forming a coating film in the case of performing a patterning treatment is described below. First, a coating film of the photosensitive coloring composition of the present invention applied to a substrate is heated (prebaked). The heating conditions vary depending on the type of each component, the mixing ratio, and the like, but are generally at 50 to 150 ° C. for about 1 to 15 minutes. Next, the prebaked coating film is irradiated with ultraviolet rays or the like via a mask having a predetermined pattern, and then developed with a developer to remove unnecessary portions to form a predetermined pattern.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, diethanolamine,
Triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4, 3,0] -5
An aqueous solution of an alkali such as nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant to the above-mentioned alkaline aqueous solution can also be used as a developer.

The developing method is a puddle method, a dipping method,
Any method such as a spray method may be used. After the development, the pattern is formed by washing with running water and air-drying with compressed air or compressed nitrogen to remove unnecessary portions. Thereafter, the pattern is subjected to heat treatment at a predetermined temperature, for example, 100 to 250 ° C. for a predetermined time by a heating device such as a hot plate or an oven, whereby a coating film having excellent heat resistance, transparency, hardness, and the like can be obtained. .

The photosensitive coloring composition of the present invention can be suitably used for a color filter used in a color liquid crystal display, a color scanner, a solid-state imaging device and the like.

The color filter is formed by arranging a color material in each pixel portion 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. Is formed.

The photosensitive coloring composition of the present invention is obtained by repeating the steps of coating, exposing, developing, and printing the photosensitive coloring composition on a substrate for each of a plurality of different colors by using the method described above. By doing so, colored pixels such as three primary colors of red, green, and blue and black used for light shielding can be formed. By using the photosensitive coloring composition of the present invention,
A color filter having excellent heat resistance, water resistance, solvent resistance and chemical resistance can be manufactured.

[0073]

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. The performance test for the prepared coating film was performed by the following method. <Performance Test and Evaluation Criteria> Storage stability: The viscosity of the red pigment dispersion obtained as described below when stored at 40 ° C. for 24 hours was measured. % Or more
And The viscosity was measured using an E-type viscometer manufactured by Tokimec. Developing properties: The coating film obtained below was exposed to 100 mJ / cm 2 with a high-pressure mercury lamp using a predetermined pattern mask.
After developing in a 0.5% by weight aqueous solution of sodium carbonate at 30 ° C., it was further washed with pure water. By these operations,
It was evaluated whether a pattern (remaining) having a line width of 20 μm was possible.パ タ ー ン indicates that patterning was possible and X indicates that patterning was impossible. Heat resistance-1: A glass plate coated and cured by the following method was heated at 280 ° C. for 30 minutes, and evaluated by a change in Y value before and after heating. 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 was measured using an Olympus microspectrophotometer OSP-SP20.
0 was used. Heat resistance-2: A glass plate coated and cured by the following 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. Chemical resistance -1: 2 using a coating film formed by the following method
After treatment in N-methyl-2-pyrrolidone at 3 ° C. for 30 minutes, the boundary surface of the liquid-immersed portion was observed. Chemical resistance-2: The coating film formed by the following method is rubbed with acetone at a load of 100 g under a condition of 25 ° C. using a rubbing tester [Taira Rika Kogyo Co., Ltd.] to reach the underlying glass substrate. The number of rubbings up to was evaluated. At this time, the number of rubbing times is less than 25 times x, 25 or more 1
Less than 00 times was evaluated as 、, and 100 times or more as ◎.

Production Example 1 [Preparation of Polymer Having Cyclocarbonate Group] Propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc) was placed in a four flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet. 4)
After adding 25.0 parts and heating the mixture to 90 ° C. while stirring, 82.5 parts of 2,3-carbonatepropyl methacrylate, 38.0 parts of methacrylic acid (hereinafter abbreviated as MAA), and benzyl methacrylate (hereinafter, benzyl methacrylate) A mixed solution of 209.5 parts of BzMA), 97.0 parts of PGMAc and 16.5 parts of t-butylperoxy-2-ethylhexanate (hereinafter abbreviated as PO) was mixed with 1
It was dropped over time. After completion of the dropwise addition, the mixture was maintained at 90 ° C. for 2 hours, and 1.7 parts of PO was added.
The acid value of the resin solids (the number of milligrams of potassium hydroxide required to neutralize the acid content present in 1 g of the sample based on the prescribed method) is 75 mg KOH / g of a carboxyl group and cyclocarbonate. A solution of the polymer (A-1) having a group was obtained. The nonvolatile content (resin weight% after drying at 107.5 ° C. for 1 hour) of the obtained resin solution was 3%.
9.4%, Gardner viscosity is T to U, polystyrene equivalent number average molecular weight is 5100, and dispersity Mw / Mn is 2.
49.

Production Example 2 [Ditto] In Production Example 1, 82.5 parts of 2,3-carbonatepropyl methacrylate was added to 26.5 parts of 3,4-carbonate butyl acrylate, and 38.0 parts of MAA was added. In 49.5 parts, 209.5 parts of BzMA were added to 25 parts of MMA.
A carboxyl group having a resin solid content of 98 mgKOH / g and a cyclocarbonate having an acid value of 98 mgKOH / g were prepared in the same manner as in Production Example 1 except that 4.0 parts and 16.5 parts of PO were changed to 3.5 parts. A polymer (A-2) having a group was obtained. The resin solution obtained had a nonvolatile content of 42.8% and a Gardner viscosity of Z.
2 to Z3, a number average molecular weight of 12000, and a dispersity M
w / Mn was 2.73.

Production Example-3 [Ditto] In Production Example-1, 38.0 parts of MAA was added to 76.0 parts, and 209.5 parts of BzMA was added to 122.0 parts of BzMA.
Part, 2-hydroxyethyl methacrylate (hereinafter HEM)
A) and carboxyl group and cyclocarbonate group having an acid value of 150 mgKOH / g in the same manner as in Production Example 1 except that 16.5 parts of styrene and 33.0 parts of styrene were used. (A-3) was obtained. The obtained resin solution had a nonvolatile content of 41.8%, a Gardner viscosity of XY, a number average molecular weight of 5,300, and a degree of dispersion Mw / Mn of 2.36.

Comparative Reference Production Example-1 [Preparation of Comparative Reference Polymer] In Production Example-1, 2,3-
BzM without using carbonate propyl methacrylate
The acid value of the resin solid content was 75 mgK in the same manner as in Production Example 1 except that 209.5 parts of A was changed to 292.0 parts.
An OH / g comparative reference polymer (H-1) was obtained. The resin solution obtained had a nonvolatile content of 40.7%, a Gardner viscosity of H, a number average molecular weight of 4900, and a dispersity of Mw / Mn.
Was 2.37.

Comparative Reference Production Example-2 [Same as above] In Production Example-1, 2,3-
Production Example 1 was repeated except that carbonate propyl methacrylate was changed to epoxycyclohexylmethyl methacrylate (Cyclomer M-100 manufactured by Daicel Chemical Industries, Ltd.) in order to prevent a gelling reaction during polymerization from 90 ° C. to 80 ° C. The reaction was performed in the same manner. Two hours after the addition of PO, the Gardner viscosity was already Z1-Z2, and the molecular weight at this point was such that the number average molecular weight was 1170.
0, the degree of dispersion Mw / Mn was 6.86, and the polymer was already a very broad molecular weight distribution. Furthermore, since the reaction solution gradually thickened, the reaction was stopped in 5 hours by adding PO, and the acid value of the resin solid content was 75 mg KOH.
/ G of Comparative Reference Polymer (H-2) was obtained. The resin solution obtained had a nonvolatile content of 40.7% and a Gardner viscosity of Z4.
-Z5, the number average molecular weight is 12700, and the degree of dispersion Mw
/ Mn was 25.59, and the polymer was further broadened in molecular weight distribution.

Production Example-3 for Comparative Reference [Same as above] In a reactor similar to Production Example-1, 400.0 mg of PGMAc was added.
After heating the mixture to 80 ° C. while stirring, 66.4 parts of methacrylic acid, 196.9 parts of MMA, 113.9 parts of glycidyl methacrylate, and 2 of PO were added.
The mixed solution with 2.6 parts was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was kept at 80 ° C. for 1 hour, and then 0.3% of PO was added.
4 parts were added and reacted at the same temperature. However, the viscosity increased during the reaction for about 3 hours after the completion of the dropwise addition of the monomer, and eventually gelled, and it was not possible to obtain [H-3] as a comparative polymer.

Example 1 Using a high-speed disperser “TSG-6H” manufactured by Igarashi Kikai,
25.0 parts of a solution of the polymer (A-1) having a carboxyl group and a cyclocarbonate group prepared in Production Example 1,
A dispersion composed of 8.0 parts of CI Pigment Red 254, 2.5 parts of Dispervic 161 and 64.5 parts of PGMAc was added to a dispersion of zirconia beads having a diameter of 0.5 mmφ for 20 minutes.
Dispersion was performed at 00 rpm for 8 hours, and a red pigment dispersion (D-
1) was obtained. Next, dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA) 7.0 was added to 100 parts of the red pigment dispersion (D-1) obtained as described above.
Parts, 0.3 parts of Irgacure # 369 and mix.
This was filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (R-1) of the present invention.

Next, 25 g of the obtained photosensitive coloring composition (R-1) was transferred into a sealed glass container and stored at 40 ° C. for 24 hours to evaluate the storage stability.

Further, the obtained photosensitive coloring composition (R-
1) is a method in which the number of rotations is 1 on a glass plate using a spin coater.
After spin-coating at 000 rpm for 9 seconds, the film was pre-dried at 60 ° C. for 5 minutes to form a coating film. Using a predetermined pattern mask on the obtained coating film, using a high-pressure mercury lamp, 100 mJ / cm
(2) After exposure, the film was developed in a 0.5 wt% aqueous solution of sodium carbonate at 30 ° C., and was further washed with pure water to evaluate whether or not a pattern with a line width of 20 μm (remaining) was possible.

Next, the obtained coating film was heated at 230 ° C. for 15 minutes to cure the coating film, and various characteristics of the coating film were evaluated. The results of these evaluations are shown in Table 1.

[0084]

[Table 1]

Examples 2 to 5 A red pigment dispersion (D-2) was prepared in the same manner as in Example 1 except that the substances shown in Table 1 were used.
To (D-3), the photosensitive coloring composition (R-
2) to (R-5) were obtained. Next, various tests were performed in the same manner, and the various performances are summarized in Table 1.

Comparative Examples 1-2 The same operation as in Example 1 was carried out except that the substances shown in Table 1 were used, and a red pigment dispersion (HD-
After blending 1) to (HD-2), photosensitive coloring compositions (HR-1) to (HR-2) were obtained. Next, various tests were performed in the same manner, and the various performances are summarized in Table 1.

[0087]

The photosensitive coloring composition of the present invention contains, as an essential component, a binder resin having a carboxyl group and an epoxy group blocked by a protecting group in order to improve the stability of the composition. Pattern formation using an alkali developing solution can be performed. In addition, by introducing a cross-linked structure by reaction with carboxyl groups and epoxy groups, it has excellent heat resistance, water resistance, solvent resistance and chemical resistance, and has extremely good stability of the composition during the process, making it practical. And a color filter having high sensitivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 4/06 C09D 4/06 G02B 5/20 101 G02B 5/20 101 G03F 7/004 505 G03F 7/004 505 7/027 502 7/027 502 7/028 7/028 F-term (reference) 2H025 AA00 AA06 AA07 AA08 AA10 AB13 AC01 AD01 BC14 BC43 BC51 CA00 CB13 CB14 CB41 CB43 CC11 FA03 FA17 FA29 2H048 BA47 BA48 PA03 BB42 PA03 4 PB25 QA12 QA17 QA22 QA23 QA24 QA25 QB14 QB19 QB23 RA03 SA01 SA21 SA31 SA41 SA51 SA62 SA64 SA83 UA01 WA01 WA02 4J038 EA011 FA012 GA06 GA07 KA04 KA08 PA17 PB08 4J100 AB02R AB03R27 AC23R37 AC23 AC23R23 AC02 AG04R AJ01Q AJ02Q AJ08Q AJ09Q AL03R AL04R AL05R AL08P AL08Q AL08R AL09R AL10R AL16P AL36Q AL39R AL41P AL44Q AL44R AM02R AM08R AM15R AM47R AM48R AQ01R AS01R AS02R AS03R AS04R BA03R BA04R BA08R BA10Q BA11R BA16Q BA31R BA75R BB17R BB18R BC04R BC08R BC12R BC28R BC43Q BC43R BC53R BC54R BC60CA04

Claims (3)

[Claims] 1. A photosensitive coloring composition comprising a polymer having an epoxy group and a carboxyl group blocked by a protecting group, a coloring material, a photopolymerizable monomer and a photopolymerization initiator as main components. 2. The photosensitive coloring composition according to claim 1, wherein the epoxy group blocked by the protecting group is a 2-oxo-1,3-dioxolan-4-yl group. 3. A color filter using the photosensitive coloring composition according to claim 1.