JP5141457B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display element. The present invention relates to a radiation-sensitive composition used for forming a colored layer, a color filter including a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

  As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (for example, patent documents) 1 and Patent Document 2). A method of forming a black matrix using a photopolymerizable composition containing a black material (see, for example, Patent Document 3) is also known.

  And in the technical field of color filters in recent years, it has become mainstream to reduce the exposure amount to shorten the tact time, and has sufficient development resistance, solvent resistance, etc. even at a low exposure amount, that is, a colored layer. There is a demand for higher sensitivity of the radiation-sensitive composition for forming. In particular, regarding solvent resistance, problems such as occurrence of cracks and chips in the pixel pattern and elution of colored components from the pixel pattern are becoming apparent, and it is required to solve them. In order to meet the recent demands for high contrast, high brightness, and high color purity for color liquid crystal display elements, various pigments used in colored layer-forming radiation-sensitive compositions have various backgrounds. It is considered that there is a tendency that the proportion of the pigment occupying in the radiation-sensitive composition for forming the colored layer tends to be higher and higher.

By the way, Patent Document 4 discloses a curable resin composition containing a polyolefin elastomer having a five-membered ring dithiocarbonate group as a curable resin composition excellent in heat resistance and the like. There is no description used for a radiation sensitive composition.
JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2005-120231 A

The subject of this invention is providing the radiation sensitive composition for colored layer formation which can form the pixel and black matrix which were excellent in solvent resistance, even if it is a low exposure amount.
Another object of the present invention is to provide a color filter having pixels formed from the radiation-sensitive composition for a color filter, and a color liquid crystal display device having the color filter.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by including a polymer having a 5-membered ring dithiocarbonate group and a functional group capable of reacting with the 5-membered ring dithiocarbonate group, thereby completing the present invention. It came to do.

  That is, the present invention firstly includes (A) a colorant, (B1) at least one group selected from the group consisting of a carboxyl group, an acid anhydride group, and a hydroxyl group, and a 5-membered ring (dithio) carbonate group. For forming a colored layer, comprising: a polymer having a polymer (hereinafter sometimes referred to as polymer (B1)), (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The present invention provides a radiation-sensitive composition (hereinafter sometimes referred to as “radiation-sensitive composition (1)”).

  The present invention secondly has (A) a colorant, (B2) at least one group selected from the group consisting of a carboxyl group, an acid anhydride group and a hydroxyl group, and a 5-membered ring (dithio) carbonate group. Polymer not having (hereinafter sometimes referred to as polymer (B2)), (B3) having a 5-membered ring (dithio) carbonate group, and having any of a carboxyl group, an acid anhydride group and a hydroxyl group. A colored layer forming sensation characterized by containing a non-polymer (hereinafter sometimes referred to as polymer (B3)), (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The present invention provides a radiation-sensitive composition (hereinafter sometimes referred to as “radiation-sensitive composition (2)”).

Thirdly, the present invention also provides a color filter comprising a colored layer formed by using the radiation-sensitive composition for forming a colored layer, and a color liquid crystal display device comprising the color filter. is there.
The “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

The radiation-sensitive composition for forming a colored layer of the present invention can form a pixel and a black matrix having excellent solvent resistance and excellent adhesion to a substrate even at a low exposure amount.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention is extremely suitable for production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state imaging devices in the electronic industry. Can be used for

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer The “colored layer” in the radiation-sensitive composition for forming a colored layer of the present invention (hereinafter sometimes simply referred to as “radiation-sensitive composition”) is used for a color filter. Means a layer composed of pixels and / or black matrix.
Hereafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

-(A) Colorant-
The colorant (A) in the present invention is not particularly limited and may be either an organic pigment or an inorganic pigment.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (CI). Listed are numbers.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

These colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include polymers described in JP-A-8-259876, various commercially available polymers or oligomers for dispersing pigments, and the like. The polymer coating method on the carbon black surface is disclosed in, for example, JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like.
The colorants can be used alone or in admixture of two or more.

When the radiation-sensitive composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development and heat resistance, (A) the coloring agent has high color development and high heat resistance. An agent, particularly a colorant having high heat decomposition resistance is preferable, specifically an organic colorant is preferable, and an organic pigment is particularly preferably used.
On the other hand, when the radiation-sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have light shielding properties, an organic pigment or carbon black is preferably used as the colorant (A).
Moreover, the radiation sensitive composition of this invention is C.I. I. Pigment red 254 and C.I. I. It is particularly preferable to contain at least one selected from the group consisting of CI Pigment Green 58 from the viewpoint of improving the solvent resistance of the colored layer formed using the radiation-sensitive composition.

  The radiation-sensitive composition of the present invention has excellent solvent resistance even when the content of the colorant is 30% by weight or more in the total solid content of the radiation-sensitive composition. In the present invention, the upper limit of the content of the colorant is preferably 70% by weight or less, particularly preferably 60% by weight or less, in the total solid content of the radiation-sensitive composition, from the viewpoint of ensuring developability. . Here, solid content is components other than the solvent mentioned later.

The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired.
As the dispersant, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, an alkylammonium salt or a phosphate ester salt of a polymer copolymer, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

  Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161 as polyurethane, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and cationic comb-type graft polymer Solsperse 24000 (manufactured by Lubrizol Corp.), Ajisper PB821, Azisper PB822, Azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.)

  These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, and particularly preferably 10 to 100 parts by weight with respect to 100 parts by weight of the (A) colorant. 50 parts by weight. In this case, when the content of the dispersant exceeds 100 parts by weight, developability and the like may be impaired.

  Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative. Specific examples include a copper phthalocyanine derivative.

-Polymer (B1)-
The polymer (B1) in the radiation-sensitive composition (1) is a component that further strengthens the coating film by undergoing a crosslinking reaction by itself during the post-baking step. Further, by introducing a carboxyl group, an acid anhydride group, a phenolic hydroxyl group or the like into the polymer (B1), alkali solubility can be imparted, and the polymer (B1) can be made into an alkali-soluble resin. The radiation-sensitive composition (1) can form a colored layer having excellent solvent resistance even when the exposure amount is low by incorporating the polymer (B1).

  The polymer (B1) includes at least one group selected from the group consisting of a carboxyl group, an acid anhydride group and a hydroxyl group (hereinafter sometimes referred to as “reactive functional group”) and a 5-membered ring (dithio). Although it is not particularly limited as long as it has a carbonate group, from the viewpoint of solvent resistance, a reactive functional group of 0.03 to 7.00 mmol / g and 5 of 0.001 to 3.000 mmol / g. It is preferably a polymer having a membered ring (dithio) carbonate group, and has a reactive functional group of 0.07 to 5.00 mmol / g and a 5-membered ring (dithio) of 0.004 to 2.000 mmol / g. A polymer having a carbonate group is more preferable.

  As the reactive functional group, a carboxyl group is preferable in terms of imparting alkali solubility. Examples of the 5-membered ring (dithio) carbonate group include a group represented by the following formula (1-1) or (1-2).

(In Formula (1-1), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In Formula (1-1) and Formula (1-2), “* "" Indicates a bond.)

In the above formula (1-1), examples of the alkyl group having 1 to 6 carbon atoms of R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Pentyl group, isopentyl group, neopentyl group, hexyl group, cyclohexyl group and the like. In the above formula (1-1), it is preferable that all of R ^{1 to} R ³ are hydrogen atoms.

  Examples of the polymer (B1) include ethylene having at least one repeating unit selected from the group consisting of repeating units represented by the following formulas (2-1) to (2-4) and a reactive functional group. And a polymer having a repeating unit derived from a polymerizable unsaturated monomer (hereinafter sometimes referred to as “monomer (b1)”).

(Wherein, R ¹ to R ³ has the same meaning as R ¹ to R ³ in formula ^{(1-1), R 4, R} 9 and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a methylene group or an alkylene group having 2 to 12 carbon atoms, R ¹⁰ represents a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, and R ^{6 to} R ⁸ are each independently a hydrogen atom or A C1-10 alkyl group, m represents 0 or 1, and n represents an integer of 1-5.

In the above formula, examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ , R ⁹ and R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Is preferred. Examples of the alkylene group having 2 to 12 carbon atoms represented by R ⁵ and R ¹⁰ include ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, nonamethylene group, decamethylene group, etc. Of these, an alkylene group having 2 to 9 carbon atoms is preferred. Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{6 to} R ⁸ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, and neopentyl group. , A hexyl group, a cyclohexyl group, an octyl group, a decanyl group, and the like. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.

In the above formula (2-1), R ⁴ is preferably a hydrogen atom or a methyl group, and R ⁵ is preferably a methylene group or an alkylene group having 2 to 9 carbon atoms.
In the above formula (2-2), R ⁶ is preferably a hydrogen atom or a methyl group, R ⁷ and R ⁸ are preferably a hydrogen atom, and n is preferably 1.
In the above formula (2-3), R ⁹ is preferably a hydrogen atom or a methyl group, and R ¹⁰ is preferably a methylene group or an alkylene group having 2 to 9 carbon atoms.
In the above formula (2-4), R ¹¹ is preferably a hydrogen atom or a methyl group.

  In the present invention, from the viewpoint of solvent resistance, the polymer (B1) has a repeating unit derived from the monomer (b1) in an amount of 3 to 95 mol% and the above formulas (2-1) to (2-4). It is preferable to contain 0.04 to 60% of the repeating unit represented, and 7 to 90 mol% of the repeating unit derived from the monomer (b1) is represented by the above formulas (2-1) to (2-4). It is more preferable to contain 0.18 to 45% of the repeating unit represented.

The polymer (B1) can be produced, for example, by the following method.
Method (1): A monomer comprising monomer (b1) and an ethylenically unsaturated monomer having an oxiranyl group (hereinafter sometimes referred to as “monomer (b2)”). A method of converting an oxiranyl group into a 5-membered ring (dithio) carbonate group after copolymerization.
Method (2): Containing monomer (b1) and an ethylenically unsaturated monomer having a 5-membered ring (dithio) carbonate group (hereinafter sometimes referred to as “monomer (b3)”). A method of copolymerizing the monomer.
A compound having a 5-membered ring (dithio) carbonate group is known to be obtained by reacting a compound having an oxiranyl group with carbon disulfide in the presence of an alkali halide such as lithium bromide (for example, In the above method (1), an oxiranyl group can be converted into a 5-membered ring (dithio) carbonate group according to this method, and the monomer (b3) is The monomer (b2) can be produced according to this known method.

As the monomer (b1), for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as 4-hydroxyphenyl (meth) acrylate;
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols;
(Meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, (meth) acrylic acid 5-hydroxypentyl ester, (meth) acrylic acid 6 -Hydroxyhexyl ester, (meth) acrylic acid 7-hydroxyheptyl ester, (meth) acrylic acid 8-hydroxyoctyl ester, (meth) acrylic acid 9-hydroxynonyl ester, (meth) acrylic acid 10-hydroxydecyl ester, ( (Meth) acrylic acid 11-hydroxyundecyl ester, (meth) acrylic acid 12-hydroxydodecyl ester (meth) acrylic acid hydroxyalkyl ester;
(Meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, (meth) acrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, (meth) acrylic acid 4- (6-hydroxyhexanoyloxy) (Meth) acrylic acid (6-) (butyl ester), (meth) acrylic acid 5- (6-hydroxyhexanoyloxy) pentyl ester, (meth) acrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester Hydroxyhexanoyloxy) alkyl ester;

(Meth) acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, (meth) acrylic acid 3- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -propyl Ester, (meth) acrylic acid 4- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -butyl ester, (meth) acrylic acid 5- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -(Meth) acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) such as pentyl ester, (meth) acrylic acid 6- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -hexyl ester ) -Alkyl esters;
(Meth) acrylic acid 4-hydroxy-cyclohexyl ester, (meth) acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, (meth) acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, (meth) acrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, (meth) acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, (meth ) Acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept-5-en-2-ylethyl ester, (meth) acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-ene 2-yl ester, (meth) acrylic acid 2-hydroxy-octahydro-4,7-methano-inden-5-yl ester (Meth) acrylic acid 2-hydroxymethyl-octahydro-4,7-methano-inden-5-ylmethyl ester, (meth) acrylic acid 2-hydroxyethyl-octahydro-4,7-methano-inden-5-yl Ethyl ester, (meth) acrylic acid 3-hydroxy-adamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxyethyl-adamantane-1 A (meth) acrylic acid hydroxyalkyl ester having an alicyclic structure such as ylethyl ester;
(Meth) acrylic acid 1,2-dihydroxyethyl ester, (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3-dihydroxypropyl ester, (meth) acrylic acid 3,4-dihydroxybutyl ester Examples include esters and (meth) acrylic acid dihydroxyalkyl esters such as 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester.

Among these monomers (b1), (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone from the viewpoint of copolymerization reactivity and easy availability. Mono (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, (meth) acrylic acid 2- (6-hydroxy) Hexanoyloxy) ethyl ester, (meth) acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, (meth) acrylic acid 4-hydroxymethyl-cyclohexylmethyl ester, (meth) 3-hydroxymethyl-adamantan-1-ylmethylacrylate Ether, 2,3-dihydroxypropyl ester (meth) acrylic acid.
A monomer (b1) can be used individually or in mixture of 2 or more types.

As the monomer (b2), for example,
(Meth) acrylic acid glycidyl, (meth) acrylic acid 2-methylglycidyl, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxyheptyl, (meth) acrylic acid 2- (Meth) acrylic acid ester having a glycidyl group such as glycidyloxyethyl, 3-glycidyloxypropyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate;
o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl Benzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4 Triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyl Oxymethyl Stille Aromatic vinyl compounds having such glycidyl group;

3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate (Meth) acrylic acid ester having an epoxycyclohexyl group such as:
Vinyl compounds having an epoxycyclohexyl group such as 1-vinyl-2,3-epoxycyclohexane and 1-vinyl-3,4-epoxycyclohexane;
Other formulas below

(In the formula, R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ represents a methylene group or an alkylene group having 2 to 12 carbon atoms.)
The compound represented by these can be mentioned.

Among these monomers (b2), the (meth) acrylic acid ester having a glycidyl group can give the repeating unit represented by the above formula (2-1), and the aromatic vinyl compound having a glycidyl group is The repeating unit represented by the above formula (2-2) can be provided, and the (meth) acrylic acid ester having an epoxycyclohexyl group can provide the repeating unit represented by the above formula (2-3). The vinyl compound having an epoxycyclohexyl group can give a repeating unit represented by the above formula (2-4).
A monomer (b2) can be used individually or in combination of 2 or more types.

As the monomer (b3),
5- (methacryloyloxy) methyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) ethyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) butyl-1,3-oxathiolane- 2-thione, 5- (methacryloyloxy) pentyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) hexyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) heptyl-1, 3-oxathiolane-2-thione, 5- (methacryloyloxy) octyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) nonyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) Dekyl-1,3-oxathiolane-2-thione, 5- (meta Liloyloxy) undecyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) dodecyl-1,3-oxathiolane-2-thione, 4,4-dimethyl-5- (methacryloyloxy) methyl-1,3- Oxathiolane-2-thione, 5- (methacryloyloxy) cyclooctyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) norbornyl-1,3-oxathiolane-2-thione, 5- (methacryloyloxy) adamantyl -1,3-oxathiolane-2-thione, 5- (acryloyloxy) methyl-1,3-oxathiolane-2-thione, 5- (acryloyloxy) ethyl-1,3-oxathiolane-2-thione, 5- ( Acryloyloxy) butyl-1,3-oxathiolane-2 Thion, 5- (acryloyloxy) pentyl-1,3-oxathiolane-2-thione, 5- (acryloyloxy) hexyl-1,3-oxathiolane-2-thione, 5- (acryloyloxy) heptyl-1,3- Oxathiolane-2-thione, 5- (acryloyloxy) octyl-1,3-oxathiolane-2-thione, 5- (acryloyloxy) nonyl-1,3-oxathiolane-2-thione, 5- (acryloyloxy) decyl- 1,3-oxathiolane-2-thione, 5- (acryloyloxy) undecyl-1,3-oxathiolane-2-thione, 5- (acryloyloxy) dodecyl-1,3-oxathiolane-2-thione, 4,4- Dimethyl-5- (acryloyloxy) methyl-1,3-oxathiolane-2-thio And other compounds obtained by converting the oxiranyl group of the monomer (b2) to a 5-membered ring (dithio) carbonate group.
Among these, 5- (methacryloyloxy) methyl-1,3-oxathiolane-2-thione is commercially available as TCMA from Kyowa Hakko Kogyo Co., Ltd.
A monomer (b3) can be used individually or in combination of 2 or more types.

In the production of the polymer (B1), the monomer (b1) and the monomer (b2), or together with the monomer (b1) and the monomer (b3), another ethylenic copolymerizable therewith An unsaturated monomer (hereinafter sometimes referred to as “monomer (b4)”) can be copolymerized.
As the monomer (b4), for example,
Maleimide;
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- N-substituted maleimides such as succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene;
Acenaphthylenes such as acenaphthylene, 5-chloroacenaphthylene, 5-hydroxymethylacenaphthylene, 5-hydroxyacenaphthylene;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) Acrylates, (meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) Alicyclic esters of (meth) acrylic acid such as acrylates;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, polyethylene glycol (n = 2 to 100) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 100) methyl ether (meth) (Meth) acrylic acid esters having an alkylene oxide structure such as acrylate and ethylene oxide modified (meth) acrylate of paracumylphenol;
Allyl (meth) acrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain, such as a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, and a poly-n-butyl (meth) acrylate macromonomer.
A monomer (b4) can be used individually or in mixture of 2 or more types.

  In the present invention, the monomer (b4) includes N-substituted maleimide, aromatic vinyl compound, acenaphthylenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic ester, (meth) acrylic. Preferred are acid aryl esters, allyl (meth) acrylates, (meth) acrylic acid esters having an alkylene oxide structure, and macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, particularly N-phenylmaleimide, N- Cyclohexylmaleimide, styrene, α-methylstyrene, acenaphthylene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene oxide modification of paracumylphenol (meth) Acryle And allyl (meth) acrylate, polystyrene macromonomer and polymethylmethacrylate macromonomer are preferred.

  In the production of polymer (B1), the copolymerization ratio of monomer (b1), monomer (b2) and monomer (b4), or monomer (b1), monomer (b3) and monomer The copolymerization ratio of the monomer (b4) can be appropriately set so that the reactive functional group and the 5-membered ring (dithio) carbonate group in the polymer (B1) have a desired content.

  Monomer (b1), copolymer of monomer (b2) and monomer (b4), or copolymer of monomer (b1), monomer (b3) and monomer (b4) For example, each monomer is converted into 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 4-methoxy-2,4-dimethylvaleronitrile) and the like in the presence of a radical polymerization initiator.

  Further, the monomer (b1), the copolymer of the monomer (b2) and the monomer (b4), or the monomer (b1), the monomer (b3) and the monomer (b4) In the polymer, each monomer is divided into 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile) and the like, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (pyrazol-1-y) Ruthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) Disulfide, bis (5-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, Produced by living radical polymerization in the presence of a molecular weight control agent that acts as an iniferter such as bisthiobenzoyl disulfide in an inert solvent, usually at a reaction temperature of 0 to 150 ° C., preferably 50 to 120 ° C. can do.

  Further, the monomer (b1), the copolymer of the monomer (b2) and the monomer (b4), or the copolymer of the monomer (b1), the monomer (b3) and the monomer (b4). The polymer can also be produced by radical polymerization of each monomer in an appropriate solvent in the presence of the above radical polymerization initiator and a polyvalent thiol compound that acts as a chain transfer agent. Here, the polyvalent thiol compound means a compound having two or more thiol groups in one molecule, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropio). Nate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryl) Oxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5, -tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione and the like.

Monomer (b1), copolymer of monomer (b2) and monomer (b4), or copolymer of monomer (b1), monomer (b3) and monomer (b4) Can be produced by polymerizing each monomer as described above and then purifying it through a reprecipitation method using two or more organic solvents having different polarities. That is, after removing insoluble impurities from the solution in a good solvent after polymerization by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution) of a precipitant (poor) Purification by pouring into the solvent) and reprecipitation of the copolymer. At that time, of the impurities remaining in the copolymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified copolymer.
Examples of the good solvent / precipitant combination used in this reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, methyl ethyl ketone / n-heptane, and the like. Can be mentioned.

The weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B1) is preferably 1,000 to 45,000. More preferably, it is 3,000 to 30,000. In this case, if the Mw is less than 1,000, the remaining film ratio of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. If it exceeds 000, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.
The ratio (Mw / Mn) of the polymer (B1) Mw and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is Preferably it is 1-5, More preferably, it is 1-4.

  In the radiation-sensitive composition (1), the polymer (B1) can be used alone or in admixture of two or more. Further, for example, JP-A-7-140654 and JP-A-10-300922 can be used. Others such as binder polymers and alkali-soluble resins disclosed in JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2008-181095, etc. It can also be used as a mixture with the above polymer.

  In the radiation sensitive composition (1), the content of the polymer (B1) is usually 5 to 1,000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. is there. In this case, if the content of the polymer (B1) is less than 5 parts by weight, the desired effect may not be obtained. On the other hand, if it exceeds 1,000 parts by weight, the pigment concentration is relatively lowered. As a result, it may be difficult to achieve the target color density.

-Polymer (B2) and polymer (B3)-
The polymer (B2) and the polymer (B3) in the radiation-sensitive composition (2) are components that further enhance the curing of the coating film by a cross-linking reaction with each other in the post-baking step. Moreover, by introducing a carboxyl group, an acid anhydride group, a phenolic hydroxyl group or the like into the polymer (B2), alkali solubility can be imparted, and the polymer (B2) can be made into an alkali-soluble resin. The radiation-sensitive composition (2) can form a colored layer having excellent solvent resistance even when the amount of exposure is low by incorporating the polymer (B2) and the polymer (B3) in combination. .

The polymer (B2) is not particularly limited as long as it has the reactive functional group described above, but from the viewpoint of solvent resistance, it is 0% relative to the total amount of the polymer (B2) and the polymer (B3). It preferably has a reactive functional group of 0.03 to 7.00 mmol / g, and more preferably has a reactive functional group of 0.07 to 5.00 mmol / g. The reactive functional group is preferably a carboxyl group in the sense of imparting alkali solubility.
Examples of the polymer (B2) include a polymer having a repeating unit derived from the monomer (b1), and more specifically, the monomer (b1) and the monomer (b4). ). The polymer (B2) preferably contains 3 to 95 mol% of repeating units derived from the monomer (b1) based on the total amount of the polymer (B2) and the polymer (B3). It is more preferable to contain 90 mol%.

The polymer (B2) can be produced in the same manner as the above-described copolymer of the monomer (b1), the monomer (b2) and the monomer (b4). Also in the polymer (B2), the monomer (b1) and the monomer (b4) are preferably the same compounds as the polymer (B1).
Moreover, as a polymer (B2), the alkali-soluble resin currently disclosed by Unexamined-Japanese-Patent No. 2008-181095 can be mentioned.

The polymer (B3) is not particularly limited as long as it has a 5-membered ring (dithio) carbonate group, but from the viewpoint of solvent resistance, the polymer (B3) is based on the total amount of the polymer (B2) and the polymer (B3). It is preferable to have a 5-membered ring (dithio) carbonate group of 0.001 to 3.000 mmol / g, and more preferable to have a 5-membered ring (dithio) carbonate group of 0.004 to 2.000 mmol / g. preferable. Examples of the 5-membered ring (dithio) carbonate group include groups represented by the above formulas (1-1) to (1-2).
Examples of the polymer (B3) include a polymer having at least one repeating unit selected from the group consisting of repeating units represented by the above formulas (2-1) to (2-4). . The polymer (B3) has a repeating unit represented by the above formulas (2-1) to (2-4) in an amount of 0.04 to 60 with respect to the total amount of the polymer (B2) and the polymer (B3). It is preferable to contain mol%, and it is more preferable to contain 0.18-45 mol%.
The polymer (B3) can be produced in the same manner as the polymer (B1) except that the monomer (b1) is not copolymerized. Also in the polymer (B3), the monomer (b4) is preferably the same compound as the polymer (B1).

The Mw and Mw / Mn of the polymer (B2) and the polymer (B3) are preferably in the same range as the polymer (B1).
In the radiation sensitive composition (2), the mixing ratio of the polymer (B2) and the polymer (B3) is preferably 95: 5 to 5:95 by weight, and 90:10 to 10:90. More preferably it is.
In the radiation-sensitive composition (2), the total content of the polymer (B2) and the polymer (B3) is usually 5 to 1,000 parts by weight with respect to 100 parts by weight of the (A) colorant. The amount is preferably 10 to 500 parts by weight. In this case, if the total content of the polymer (B2) and the polymer (B3) is less than 5 parts by weight, the desired effect may not be obtained. Since the density is lowered, it may be difficult to achieve a target color density as a thin film.

-(C) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As such a polyfunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol, and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both end hydroxyl polymers such as both end hydroxypoly-1,3-butadiene, both end hydroxypolyisoprene, both end hydroxypolycaprolactone;
Tris [2- (meth) acryloyloxyethyl] phosphate,
Isocyanuric acid ethylene oxide modified triacrylate;
Examples thereof include poly (meth) acrylate having a urethane structure.

Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols, their dicarboxylic acid-modified products, and poly (meth) acrylates having a urethane structure are preferred. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate and succinic acid Monoesterified product with dipentaerythritol Preferred are monoesterified products of taacrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, and particularly trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Monoesterified product of hexaacrylate, pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of colored layer, excellent surface smoothness of colored layer, and unexposed This is preferable in that ground stains, film residue, and the like hardly occur on the substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The content of the polyfunctional monomer in the present invention is usually 10 to 1,000 parts by weight, preferably 20 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. In this case, if the content of the polyfunctional monomer is less than 10 parts by weight, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, if it exceeds 1,000 parts by weight, for example, alkali developability is reduced. In addition, there is a tendency that background stains, film residue, etc. are likely to occur on the substrate in the unexposed area or on the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] ester of acid; mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinyl Indole, N-vinylindoline, N-vinylbenzimidazole, N-vinylcal N-vinyl nitrogen-containing heterocyclic compounds such as azole, N-vinyl piperidine, N-vinyl piperazine, N-vinyl morpholine, N-vinyl phenoxazine; in addition to N- (meth) acryloyl morpholine, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more.

  The content ratio of the monofunctional monomer in the present invention is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the pixel tend to be lowered.

-(D) Photopolymerization initiator-
The photopolymerization initiator (D) in the present invention is a monofunctional monomer used in combination with the (C) polyfunctional monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active species capable of initiating polymerization of a functional monomer.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds is preferred.

  In the present invention, the general content of the photopolymerization initiator is usually 0.01 to 120 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the (C) polyfunctional monomer. is there. In this case, if the content of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 120 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) ) -1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1,2-octanedione, etc. Can be mentioned.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 1,2-octanedione and the like are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, the content when an acetophenone-based compound is used as the photopolymerization initiator is usually 0.01 to 85 parts by weight, preferably 1 with respect to 100 parts by weight of the (C) polyfunctional monomer. It is -75 weight part, More preferably, it is 1-65 weight part. In this case, if the content of the acetophenone compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, On the other hand, when it exceeds 85 parts by weight, the formed colored layer tends to be detached from the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 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 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned. .

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is preferred.

These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the content in the case of using a biimidazole compound as a photopolymerization initiator is usually 0.01 to 40 parts by weight, preferably 100 parts by weight of (C) polyfunctional monomer, 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the content of the biimidazole compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the developed colored layer tends to fall off from the substrate or the surface of the colored layer tends to come off during development.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-bis. (Diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

  In the present invention, the content when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of (C) polyfunctional monomer. 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity tends to be reduced. On the other hand, if the content exceeds 40 parts by weight, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

  The amine-based hydrogen donor can function as a sensitizer when used in combination with a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound. When an amine-based hydrogen donor is used as a sensitizer, the content thereof is usually 300 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of a photopolymerization initiator other than a biimidazole compound. The amount is preferably 100 parts by weight or less, but if the content is too small, it is difficult to obtain a sufficient effect. Therefore, the lower limit of the content is preferably 2 parts by weight, more preferably 5 parts by weight.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, the content when using a triazine compound as a photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of (C) polyfunctional monomer. 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the triazine compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

  Specific examples of the O-acyloxime compound include 1,2-heptanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (benzoyl) phenyl]-, 2- (O-benzoyloxime), ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (3- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl)-, 1- O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl- 6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5) -Tetrahydropyranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4 (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl) -4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- 3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxy) Cibenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1, 3-Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

Among these O-acyloxime compounds, in particular, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the content when an O-acyloxime compound is used as the photopolymerization initiator is preferably 0.01 to 85 parts by weight with respect to 100 parts by weight of the (C) polyfunctional monomer, More preferably, it is 1-75 weight part, Most preferably, it is 1-65 weight part. In this case, if the content of the O-acyloxime compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 85 parts by weight, the formed colored layer tends to be detached from the substrate during development.

-Additives-
The radiation-sensitive composition of the present invention can contain various additives as necessary.
Examples of the additive include a polyfunctional epoxy compound. The polyfunctional epoxy compound reacts with the sulfanyl group produced as a result of the crosslinking reaction of the polymer (B1) or the sulfanyl group produced as a result of the crosslinking reaction between the polymer (B2) and the polymer (B3). Further strengthen the curing. Examples of the polyfunctional epoxy compound include aromatic epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy resin; alicyclic epoxy Other epoxy resins such as resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils; brominated derivatives of these epoxy resins, epoxidized products of (co) polymers of butadiene, Examples include epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl group-containing unsaturated compounds, and triglycidyl isocyanurate.

  Other additives include, for example, fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic surfactants Surfactant such as an agent; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Examples thereof include an aggregation inhibitor such as sodium acrylate.

-Solvent-
The radiation-sensitive composition of the present invention contains the components (A) to (D) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent. The
As said solvent, (A)-(D) component which comprises a radiation sensitive composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. Can be appropriately selected and used.

As such a solvent, for example,
Alcohols such as methanol, ethanol, benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly) alkylene glycol monoalkyl ethers such as monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol from the viewpoints of solubility, pigment dispersibility, coatability, etc. Mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate 1,3-butylene glycol diacetate, N-butyl acid, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, 3-methoxypropion Ethyl acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

Color filter The color filter of the present invention comprises a colored layer formed from the radiation-sensitive composition of the present invention.
The method for forming the color filter of the present invention will be described below.
First, on the surface of the substrate, if necessary, a radiation-sensitive composition in which a light shielding layer (black matrix) is formed so as to partition a pixel forming portion, and a red pigment, for example, is dispersed on the substrate. After applying the liquid composition of the product, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
The black matrix can be formed using the radiation-sensitive composition of the present invention in the same manner as in the pixel formation.

Examples of the substrate used when forming the pixel include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is generally a 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The color filter of the present invention thus obtained has excellent solvent resistance and is extremely useful for high-definition color liquid crystal surface elements, color imaging tube elements, color sensors, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Red 254 (trade name BK-CF, manufactured by Ciba Specialty Chemicals) /C.I. I. Pigment Red 177 = 20 parts by weight of 80/20 (weight ratio) mixture, 5 parts by weight of Disperbyk-2001 as a dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 25% Then, a pigment dispersion (R) was prepared by treatment with a bead mill.

Preparation Example 2
(A) C.I. I. Pigment green 58 / C.I. I. Pigment Yellow 150 = 50/50 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Solsperse 24000 as a dispersing agent, and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill to obtain a pigment dispersion (G) Was prepared.

Preparation Example 3
(A) C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 90/10 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Solsperse 24000 as a dispersing agent, and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill to obtain a pigment dispersion (B) Was prepared.

Synthesis of polymer Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of cyclohexanone, followed by 15 parts by weight of methacrylic acid, 5- (methacryloyloxy) methyl-1,3. -15 parts by weight of oxathiolane-2-thione, 10 parts by weight of n-butyl methacrylate, 60 parts by weight of benzyl methacrylate, and 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator were charged and purged with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer solution. This polymer is referred to as “polymer (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of cyclohexanone, followed by 15 parts by weight of methacrylic acid, 5- (methacryloyloxy) methyl-1,3. -15 parts by weight of oxathiolane-2-thione, 10 parts by weight of n-butyl methacrylate, 20 parts by weight of N-phenylmaleimide, 10 parts by weight of styrene, 30 parts by weight of benzyl methacrylate, and 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator Was replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer solution. This polymer is referred to as “polymer (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of cyclohexanone, followed by 15 parts by weight of methacrylic acid, 5- (methacryloyloxy) methyl-1,3. -15 parts by weight of oxathiolane-2-thione, 10 parts by weight of n-butyl methacrylate, 20 parts by weight of 2-hydroxyethyl methacrylate, 40 parts by weight of benzyl methacrylate, and 3 parts of α-methylstyrene dimer as a molecular weight regulator, Replaced. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer solution. This polymer is referred to as “polymer (B-3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of cyclohexanone, followed by 15 parts by weight of methacrylic acid, 5- (methacryloyloxy) methyl-1,3. -15 parts by weight of oxathiolane-2-thione, 10 parts by weight of n-butyl methacrylate, 20 parts by weight of N-phenylmaleimide, 10 parts by weight of styrene, 20 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of benzyl methacrylate, and molecular weight regulator Was charged with 3 parts by weight of α-methylstyrene dimer and substituted with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer solution. This polymer is referred to as “polymer (B-4)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of cyclohexanone, and then 5- (methacryloyloxy) methyl-1,3-oxathiolane-2-thione. 15 parts by weight, 10 parts by weight of n-butyl methacrylate, 20 parts by weight of N-phenylmaleimide, 10 parts by weight of styrene, 45 parts by weight of benzyl methacrylate, and 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator were substituted with nitrogen. did. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer solution. This polymer is referred to as “polymer (B-5)”.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of cyclohexanone, followed by 15 parts by weight of methacrylic acid, 10 parts by weight of n-butyl methacrylate, and N-phenyl. 20 parts by weight of maleimide, 10 parts by weight of styrene, 20 parts by weight of 2-hydroxyethyl methacrylate, 25 parts by weight of benzyl methacrylate, and 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator were charged and purged with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer solution. This polymer is referred to as “polymer (B-6)”.

Example 1
Preparation of radiation-sensitive composition (A) 100 parts by weight of pigment dispersion (R) as a colorant, 20 parts by weight of polymer (B-1) (in terms of solid content), (C) difunctional as a polyfunctional monomer 10 parts by weight of pentaerythritol hexaacrylate and 5 parts by weight of trimethylolpropane triacrylate, (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 5 as a photopolymerization initiator A liquid composition having a solid content concentration of 25% was prepared by mixing parts by weight, 3 parts by weight of 4,4′-bis (diethylamino) benzophenone, and cyclohexanone as a solvent.
The obtained radiation-sensitive composition was evaluated according to the following procedure. The evaluation results are shown in Table 2.

Evaluation of solvent resistance The obtained liquid composition was applied to a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater, and then applied on a hot plate at 90 ° C. 4 Pre-baking was performed for 5 minutes to form five coating films having a film thickness after pre-baking of 2.5 μm.
Then, after cooling these substrates to room temperature, the coating film was irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm of 500, 750, and 1,000 J / m ² through a photomask using a high-pressure mercury lamp. It exposed with the exposure amount. Thereafter, after developing a developing solution composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) on these substrates, shower development was performed for 1 minute. Further, post baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm dot pattern on the substrate.
The obtained substrate was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. As a result, when the film thickness ratio before and after immersion (film thickness after immersion × 100 / film thickness before immersion) is 95% or more and N-methylpyrrolidone after immersion is not colored at all, ○ The case where the film thickness ratio before and after is less than 95% or the N-methylpyrrolidone after the immersion is slightly colored, the case where a pixel pattern in which cracks occur after the immersion or peeling from the substrate is observed X, evaluated as

Evaluation of Adhesion The obtained liquid composition was applied on the surface of a glass substrate using a spin coater and then pre-baked at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m ² without using a high pressure mercury lamp. did. Thereafter, a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. was discharged onto the coating film at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 1 minute, and then at 220 ° C. for 30 minutes. Post bake was performed. Next, according to the JIS K5400 standard, the cured film is cross-cut into 100 grids, and adhesion is evaluated. When the grids are not peeled off, 1 or 10 of the grids are peeled off. The case was evaluated as Δ, and the case where more than 10 grids were peeled off was evaluated as ×.

Examples 2 to 25 and Comparative Examples 1 to 5
In Example 1, a radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type and content (parts by weight) of each component were changed as shown in Table 1.
Subsequently, various evaluation was performed like Example 1 using the obtained radiation sensitive composition. The results are shown in Table 2.

In Table 1, each component is as follows.
C-1: Dipentaerythritol hexaacrylate C-2: Trimethylolpropane triacrylate D-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
D-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
D-3: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-4: 2,4-diethylthioxanthone D-5: 4,4′-bis (diethylamino) benzophenone E-1: bisphenol A novolac type epoxy resin (trade name 157S65, manufactured by Japan Epoxy Resins Co., Ltd.)

  As is apparent from Tables 1 and 2, the polymer (B1), [(B-1) to (B-4)] or a combination of the polymer (B2) and the polymer (B3) [(B-5 ) To (B-6)], the coating film formed using the radiation-sensitive composition is excellent in solvent resistance and excellent in adhesion to the substrate even at a low exposure amount. .

Claims (6)

  (A) a colorant, (B1) a polymer having at least one group selected from the group consisting of a carboxyl group, an acid anhydride group and a hydroxyl group, and a 5-membered ring (dithio) carbonate group, (C) polyfunctional A radiation-sensitive composition for forming a colored layer, comprising a polymerizable monomer and (D) a photopolymerization initiator.   (A) a colorant, (B2) a polymer having at least one group selected from the group consisting of a carboxyl group, an acid anhydride group and a hydroxyl group, and having no 5-membered ring (dithio) carbonate group, (B3 ) A polymer having a 5-membered ring (dithio) carbonate group and having no carboxyl group, acid anhydride group or hydroxyl group, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A radiation-sensitive composition for forming a colored layer, comprising: The radiation-sensitive composition for forming a colored layer according to claim 1 or 2, wherein the 5-membered ring (dithio) carbonate group is a group represented by the following formula (1-1) or (1-2).

(In Formula (1-1), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In Formula (1-1) and Formula (1-2), “* "" Indicates a bond.) The 5-membered ring (dithio) carbonate group is introduced by at least one repeating unit selected from the group consisting of repeating units represented by the following formulas (2-1) to (2-4). A radiation-sensitive composition for forming a colored layer.

(Wherein, R ¹ to R ³ has the same meaning as R ¹ to R ³ in formula ^{(1-1), R 4, R} 9 and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a methylene group or an alkylene group having 2 to 12 carbon atoms, R ¹⁰ represents a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, and R ^{6 to} R ⁸ are each independently a hydrogen atom or A C1-10 alkyl group, m represents 0 or 1, and n represents an integer of 1-5.   The color filter provided with the colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-4.   A color liquid crystal display device comprising the color filter according to claim 5.