TWI450035B - Radiation sensitive composition for forming colored layer, color filter, color liquid crystal display element and method for producing an alkali soluble resin - Google Patents

Description

Radiation-sensitive composition for forming a color layer, color filter, color liquid crystal display element, and method for producing an alkali-soluble resin

The present invention relates to radiation sensitive compositions, color filters, and color liquid crystal display elements for forming color layers. In particular, it relates to a radiation-sensitive composition for forming a color layer that can be used in a transmissive or reflective type color liquid crystal display, a color photographic tube device, or the like, having a color formed using the radiation-sensitive composition. A color filter of a layer and a color liquid crystal display element including the color filter.

As a conventional method of manufacturing a color filter using a color radiation-sensitive composition, a method is known in which a color radiation-sensitive composition is applied to a substrate or a substrate on which a light-blocking layer of a desired pattern has been previously formed, which is applied. The composition is dried, and the dried coating is exposed to radiation in a desired pattern shape (hereinafter referred to as "exposure") and developed to obtain pixels of each color (see Japanese Patent Laid-Open Publication Nos. 2-144502 and 3-53201). .

In addition, in the field of color filters in recent years, the takt time is mainly shortened by reducing the exposure amount, and the pixel and black matrix formed at a low exposure amount require an excellent pattern shape and solvent resistance. And adhesion to the substrate. Meanwhile, Japanese Patent Laid-Open Publication Nos. 10-31308 and 10-300922 propose to incorporate a copolymer of an N-position substituted maleimide monomer in a color radiation-sensitive composition to improve developability and heat resistance. . However, with such a color radiation-sensitive composition, it is difficult to obtain a pixel having a good pattern shape and a black matrix while shortening the adhesive time. When the exposure amount is lowered, the adhesion to the substrate after development is insufficient, so that the film retention percentage is lowered, the pattern is broken or the side etching or the pattern is peeled off from the substrate.

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel radiation-sensitive composition for forming a color layer which does not reduce the percentage of film retention and pattern breakage and side etching even at low exposure, providing solvent resistance and adhesion to the substrate. Pixels and black matrices of excellent properties and other properties, and exhibit excellent storage stability as a liquid composition even when containing a high concentration of pigment.

Another object of the present invention is to provide a color filter having a color layer formed from the radiation-sensitive composition of the present invention and a color liquid crystal display element comprising the color filter.

Other objects and advantages of the invention will be apparent from the description.

According to the present invention, the above objects and advantages of the present invention are first achieved by a radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) A photopolymerization initiator which is used to form a color layer, the alkali-soluble resin (B) comprising a regenerating unit represented by the following formula (1) having at least one group selected from the group consisting of an acid functional group and an acid anhydride group: (wherein R ⁷ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms), and a group represented by the following formula (2): (wherein X represents an n-valent organic group, R ⁸ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, n represents an integer of 2 to 10, and " ^* " represents a bond) The polymer.

In the present invention, the color layer means "a layer including pixels and/or black matrices".

According to the present invention, secondly, the objects and advantages of the present invention are achieved by a color filter comprising a color layer formed using the radiation-sensitive composition of the present invention.

According to the present invention, third, the objects and advantages of the present invention described above are attained by a color liquid crystal display element comprising the color filter described above.

Best mode for carrying out the invention

The invention is described in detail below.

- (A) colorant -

The coloring agent in the present invention is not particularly limited in color, and is appropriately selected depending on the use of the color filter to be produced, and may be any of a pigment, a dye or a natural coloring agent.

Since the color filter requires high color rendering property and heat resistance, the coloring agent in the present invention is preferably a coloring agent having high color rendering property and high heat resistance, especially a coloring agent having high heat decomposition resistance. . It is preferred to use an organic pigment or an inorganic pigment, and it is particularly preferable to use an organic pigment or carbon black.

Examples of the foregoing organic pigments include compounds classified as "pigments" according to a color index, in detail, compounds having the following color index (CI) numbers, namely: CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14. CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180 and CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73 and CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31 C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI pigment red 254, CI pigment red 255, CI pigment red 262, CI pigment red 264 and CI pigment red 272; CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36 and CI pigment violet 38; CI pigment blue 15, CI pigment blue 15:3, CI pigment blue 15:4, CI pigment blue 15:6, CI pigment blue 60 and CI pigment blue 80; CI pigment green 7 , CI Pigment Green 36 and CI Pigment Green 58; CI Pigment Brown 23 and CI Pigment Brown 25; and CI Pigment Black 1 and CI Pigment Black 7.

These organic pigments may be purified and used as needed by, for example, a sulfuric acid recrystallization method, a solvent cleaning method, a salt milling method, or a combination of these methods.

Preferred among these organic pigments are at least one pigment selected from the group consisting of CI Pigment Yellow 83, CI Pigment Yellow 139, CI Pigment Yellow 138, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Red 166, CI Pigment Red. 177, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Violet 23, C.I. Pigment Blue 60 and C.I. Pigment Blue 80.

In addition, illustrative examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, iron blue, oxidation. Chrome green, cobalt, amber, titanium black, synthetic iron black and carbon black.

In the present invention, the aforementioned organic pigments and inorganic pigments may be used singly or in combination of two or more kinds or in combination. When forming a pixel, it is preferred to use at least one organic pigment. When forming a black matrix, it is preferred to use two or more organic pigments and/or carbon black.

In the present invention, the surface of the pigment particles may be modified with a polymer before use as needed. Examples of the polymer used for the surface modification of the pigment particles include the polymers described in Japanese Patent Laid-Open Publication No. 8-259876 and other publications, and various commercially available polymers or oligomers used for dispersing pigments.

In the present invention, the colorant may optionally be used together with a dispersing agent.

As the dispersing agent, for example, a suitable cationic, anionic, nonionic or amphoteric dispersing agent can be used. It is preferred to use a polymeric dispersant. Specific examples thereof include modified acrylic copolymers, acrylic copolymers, polyurethanes, polyesters, alkylammonium or phosphate salts of copolymers, and cationic comb-like graft polymers. The cationic comb-like graft polymer is a polymer in which a branched polymer of two or more molecules is grafted to a molecule of a backbone polymer having a plurality of basic groups (cationic functional groups), and is exemplified. It is a polymer comprising a polyethylenimine as a backbone polymer and an ε-caprolactone ring-opening polymer as a branched polymer. Such dispersion Among the agents, modified acrylic copolymers, polyurethanes, and cationic comb-like graft polymers are preferred.

These dispersants are commercially available products. Specific examples of commercially available dispersant products include Disperbyk-2000 and Disperbyk-2001 (products of BYK Japan KK) as modified acrylic copolymers, Disperbyk-161, Disperbyk-162, Disperbyk as polyurethanes -165, Disperbyk-167, Disperbyk-170 and Disperbyk-182 (product of BYK Japan KK) and Solsperse 76500 (product of Lubrizol Japan Ltd.) and Solsperse 24000 and Solsperse 37500 (Lubrizol) as cationic comb-like graft polymers Products of Japan Ltd.) and AJISPER PB821, AJISPER PB822 and AJISPER PB880 (products of Ajinomoto Fine-Techno.Co., Inc.)

These dispersants may be used singly or in combination of two or more. The content of the dispersant is usually not more than 100 parts by weight, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly preferably 10 to 50, based on 100 parts by weight of the coloring agent (A). Parts by weight. In this case, when the dispersant content exceeds 100 parts by weight, developability and the like may be impaired.

- (B) alkali soluble resin -

The alkali-soluble resin in the present invention comprises a polymer having at least one group selected from the group consisting of an acid functional group and an acid anhydride group, a reproducing unit represented by the above formula (1), and a group represented by the above formula (2) (hereinafter referred to as "Polymer B"). The alkali-soluble resin acts as a binder on the colorant (A) and can be formed The color developing layer is dissolved in the alkali developer in the developing step.

In the above formula (1), illustrative examples of the alkyl group having 1 to 12 carbon atoms as R ⁷ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and second. Butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl and cyclohexyl. On the other hand, illustrative examples of the aryl group having 6 to 12 carbon atoms as R ⁷ include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. . As R ⁷ in the above formula (1), a cyclohexyl group, a phenyl group or the like is preferred, and a phenyl group is particularly preferred.

An illustrative example of the group represented by the above formula (2) includes a group represented by the following formula (3): (wherein Y represents an n-valent organic group, R ⁸ and n are as defined in formula (2), and " ^* " is a bond).

In the above formulas (2) and (3), the alkylene group having 2 to 6 carbon atoms as R ⁸ is preferably a linear alkyl group having 2 to 6 carbon atoms, and the following formula (R8) Show group: (wherein R ¹⁰ represents a single bond, a methylene group or a linear alkyl group having 2 to 4 carbon atoms, and " ^* " means a bond to be bonded to S), or the like.

Further, in the above formulas (2) and (3), n is preferably from 2 to 8, more preferably from 2 to 6. Further, in the above formula (3), Y is preferably an alkylene group having 2 to 20 carbon atoms, any of the groups represented by the following formulas (Y-1) to (Y-6) or the like.

(In the formula (Y-1), R ¹¹ represents an exoethyl or a propyl group, and m represents an integer of 1 to 20; in the formula (Y-6), R ¹² each independently represents 2 to 6 carbons. A methylene group or an alkyl group of an atom; in all the former formulas, " ^* " means a bond.)

An illustrative example of the polymer (B) includes a compound comprising (b1) at least one member selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and an unsaturated phenol compound (hereinafter referred to as "unsaturated compound (b1)"). And (b2) a compound represented by the following formula (4) (hereinafter referred to as "unsaturated compound (b2)": (wherein R7 is as defined in the formula (1)), a copolymer obtained by polymerizing a polymerizable mixture in the presence of a compound represented by the following formula (5) (hereinafter referred to as "copolymer (B1)": (where X, R ⁸ and n are as defined by formula (2)).

In the unsaturated compound (b1), illustrative examples of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acid An acid or an anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, isaconic acid, isaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; having three or more a carboxyl group-unsaturated polycarboxylic acid or an anhydride thereof; a mono[(meth)acryloxyalkylalkyl] ester of a polycarboxylic acid having two or more carboxyl groups, such as succinic acid mono [2-(methyl) acrylonitrile] Oxyethyl] ester and mono [2-(methyl) propylene oxyethyl] phthalic acid ester; and mono (meth) acrylate having a carboxyl group and a hydroxyl group polymer at both ends, such as ω-carboxyl group Polycaprolactone mono(meth)acrylate.

Among these unsaturated carboxylic acids and unsaturated carboxylic anhydrides, the commercial trademarks of succinic acid mono [2-propenyl oxyethyl] ester and phthalic acid mono [2- propylene oxy oxy] ester are individually Light Ester HOA. - MS and Light Ester HOA-MPE (product of Kyoeisha Chemical Co., Ltd.).

Illustrative examples of the aforementioned unsaturated phenolic compound include unsaturated phenols such as o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4 -vinylphenol, o-isopropenylphenol, m-isopropenylphenol and p-isopropenylphenol; and unsaturated naphthols such as 2-vinyl-1-naphthol, 3-vinyl-1- Naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol and 3-isopropenyl-1-naphthol.

In the present invention, as the unsaturated compound (b1), (meth)acrylic acid, p-vinylphenol, and the like are preferred, and (meth)acrylic acid is particularly preferred.

Illustrative examples of the unsaturated compound (b2) include N-phenyl maleimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl-butylene Imine, N-p-hydroxyphenyl maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-amber quinone imine 3-methyleneimine benzyl ester, N-succinimide-4-butylimide butyrate, N-succinimide-6-butylene Aminohexanoate, N-succinimide-3-butylimide, propionate and N-(acridinyl) maleimide.

Of these N-position substituted maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, and the like, and N-benzene The cis-butenylenediamine is particularly preferred.

In the copolymer (B1), the unsaturated compound (b2) may be used singly or in combination of two or more.

In the present invention, the polymerizable mixture for synthesizing the copolymer (B1) may contain, in addition to the unsaturated compound (b1) and the unsaturated compound (b2), other unsaturated compounds copolymerizable with the compounds.

The other unsaturated compound (b3) is at least one selected from the group consisting of unsaturated compounds having an oxetane skeleton (hereinafter referred to as "unsaturated compound (b3-1)" and unsaturated compounds having a tetrahydrofuran skeleton (hereinafter A compound called "unsaturated compound (b3-2)") (hereinafter collectively referred to as "unsaturated compound (b3)") is preferred.

Preferable examples of the unsaturated compound (b3-1) include a compound represented by the following formula (I) (hereinafter referred to as "unsaturated compound (b3-1a)") and a compound represented by the following formula (II) (hereinafter referred to as "Unsaturated compound (b3-1b)").

(In the formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an n system Is an integer from 0 to 6.)

(In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are as in the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ And the definition of n).

Illustrative examples of the alkyl group having 1 to 4 carbon atoms of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in} the formula (I) and the formula (II) include a methyl group, an ethyl group, and N-propyl, isopropyl, n-butyl, isobutyl, t-butyl and tert-butyl.

Further, illustrative examples of the fluoroalkyl group having 1 to 4 carbon atoms of R ³ , R ⁴ , R ⁵ and R ⁶ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a 1-fluoroethyl group. , 2-fluoroethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, nonafluoro-positive Butyl, nonafluoro-isobutyl, nonafluoro-t-butyl and nonafluoro-t-butyl.

Further, illustrative examples of the aryl group having 6 to 20 carbon atoms of R ³ , R ⁴ , R ⁵ and R ⁶ include a phenyl group, an o-tolyl group, a m-tolyl group and a p-tolyl group.

Specific examples of the unsaturated compound (b3-1a) include (meth) acrylate such as 3-[(meth) propylene 醯 oxymethyl] oxetane, 3-[(meth) propylene oxime Methyl]-2-methyloxetane, 3-[(meth)acrylomethoxymethyl]-3-methyloxetane, 3-[(meth)acrylomethoxymethyl ]-2-Ethyloxetane, 3-[(meth)acrylomethoxymethyl]-3-ethyloxetane, 3-[(methyl)acryloxymethyl]- 2-trifluoromethyloxetane, 3-[(meth)acrylomethoxymethyl]-2-pentafluoroethyloxetane, 3-[(meth)acrylomethoxymethyl ]-2-phenyloxetane, 3-[(meth)acrylomethoxymethyl]-2,2-difluorooxetane, 3-[(meth)acrylomethoxymethyl -2,2,4-trifluorooxetane, 3-[(methyl)acryloxymethyl]-2,2,4,4-tetrafluorooxetane, 3-[2 -(Meth)acryloyloxyethyl]oxetane, 3-[2-(methyl)propenyloxyethyl]-2-methyloxetane, 3-[2-(A Base) propylene oxiranyl ethyl]-3-methyl oxetane, 3-[2-(methyl) propylene oxime Ethyl]-2-ethyloxetane, 3-[2-(methyl)acryloyloxyethyl]-3-ethyloxetane, 3-[2-(methyl)propene醯Oxyethyl]-2-trifluoromethyl oxetane, 3-[2-(methyl) propylene oxyethyl]-2-pentafluoroethyl oxetane, 3-[2 -(Methyl)acryloyloxyethyl]-2-phenyloxetane, 3-[2- (Meth)acryloyloxyethyl]-2,2-difluorooxetane, 3-[2-(methyl)propenyloxyethyl]-2,2,4-trifluorooxocyclo Butane and 3-[2-(methyl)acryloyloxyethyl]-2,2,4,4-tetrafluorooxetane.

Further, specific examples of the unsaturated compound (b3-1b) include (meth) acrylate such as 2-[(meth) propylene 醯 oxymethyl] oxetane, 2-[(meth) propylene醯oxymethyl]-2-methyloxetane, 2-[(meth)acrylomethoxymethyl]-3-methyloxetane, 2-[(meth) propylene oxime Methyl]-4-methyloxetane, 2-[(meth)acrylomethoxymethyl]-2-ethyloxetane, 2-[(meth)acrylomethoxymethyl ]-3-ethyloxetane, 2-[(meth)acrylomethoxymethyl]-4-ethyloxetane, 2-[(methyl)acryloxymethyl]- 2-trifluoromethyloxetane, 2-[(meth)acrylomethoxymethyl]-3-trifluoromethyloxetane, 2-[(meth)acrylomethoxymethyl ]-4-trifluoromethyloxetane, 2-[(meth)acrylomethoxymethyl]-2-pentafluoroethyloxetane, 2-[(methyl)propene oxime Methyl]-3-pentafluoroethyl oxetane, 2-[(meth)acrylomethoxymethyl]-4-pentafluoroethyl oxetane, 2-[(meth) propylene醯oxymethyl]-2-phenyloxetane, 2-[( Methyl)propenyloxymethyl]-3-phenyloxetane, 2-[(meth)acrylomethoxymethyl]-4-phenyloxetane, 2-[(methyl ) propylene oxime methyl]-2,3-difluorooxetane, 2-[(meth) propylene oxime methyl]-2,4-difluorooxetane, 2-[( Methyl)propenyloxymethyl]-3,3-difluorooxetane, 2-[(methyl)acryloxymethyl]-3,4-difluorooxetane, 2- [(Meth)acrylomethoxymethyl]-4,4-difluorooxetane, 2-[(methyl)acryloxymethyl]-3,3,4-trifluorooxetane Alkane, 2-[(meth)acrylofluorene -3,4,4-trifluorooxetane, 2-[(meth)acrylomethoxymethyl]-3,3,4,4-trifluorooxetane, 2-[ 2(Meth)acryloyloxyethyl]oxetane, 2-[2(methyl)acryloyloxyethyl]-2-methyloxetane, 2-[2(methyl) Propylene oxiranyl ethyl]-3-methyloxetane, 2-[2(methyl)acryloyloxyethyl]-4-methyloxetane, 2-[2(methyl) Propylene oxiranyl ethyl]-2-ethyloxetane, 2-[2(methyl)acryloyloxyethyl]-3-ethyloxetane, 2-[2(methyl) Propylene oxiranyl ethyl]-4-ethyloxetane, 2-[2(methyl)acryloyloxyethyl]-2-trifluoromethyloxetane, 2-[2 (a Base) propylene oxiranyl ethyl]-3-trifluoromethyl oxetane, 2-[2(methyl) propylene oxyethyl]-4-trifluoromethyl oxetane, 2- [2(Methyl) propylene oxiranyl]-2-pentafluoroethyl oxetane, 2-[2(methyl) propylene oxyethyl]-3-pentafluoroethyl oxetane Alkane, 2-[2(methyl)acryloyloxyethyl]-4-pentafluoroethyloxetane, 2-[2(methyl)acryloyloxyethyl]-2 -phenyloxetane, 2-[2(methyl)acryloyloxyethyl]-3-phenyloxetane, 2-[2(methyl)acryloxyethyl]-4 -phenyloxetane, 2-[2(methyl)acryloyloxyethyl]-2,3-difluorooxetane, 2-[2(methyl)acryloyloxyethyl] -2,4-difluorooxetane, 2-[2(methyl)acryloyloxyethyl]-3,3-difluorooxetane, 2-[2(methyl)propene oxime Oxyethyl]-3,4-difluorooxetane, 2-[2(methyl)acryloyloxyethyl]-4,4-difluorooxetane, 2-[2(A Base) propylene oxiranyl ethyl]-3,3,4-trifluorooxetane, 2-[2(methyl)propene oxiranyl]-3,4,4-trifluorooxetane Alkane and 2-[2(methyl)acrylomethoxyethyl]-3,3,4,4-tetrafluorooxetane.

Among these unsaturated compounds (b3-1a) and unsaturated compounds (b3-1b), 3-[(meth)acrylomethoxymethyl]oxetane, 3-[(meth)acrylofluorene oxide Methyl]-3-ethyloxetane, 3-[(meth)acrylomethoxymethyl]-2-trifluoromethyloxetane, 3-[(methyl)propene oxime Methyl]-2-phenyloxetane, 2-[(meth)acrylomethoxymethyl]oxetane and 2-[(methyl)acryloxymethyl]-4-tri Fluoromethyloxetane is preferred, and 3-[(meth)acrylomethoxymethyl]oxetane, 3-[(meth)acrylomethoxymethyl]-3-ethyloxy Heterocyclobutane, 3-[(meth)acrylomethoxymethyl]-2-trifluoromethyloxetane, 3-[(meth)acrylomethoxymethyl]-2-phenyloxy Heterocyclobutane, 2-[(meth)acrylomethoxymethyl]oxetane and 2-[(meth)acrylomethoxymethyl]-4-trifluoromethyloxetane Preferably, the chemical resistance of the color layer to be produced is improved because the development tolerance of the radiation-sensitive composition to be prepared is broadened.

Further, in the present invention, in addition to the saturated compound (b3-1a) and the unsaturated compound (b3-1b), an (oxetanyl)ether of a vinylphenol such as (3-oxetanyl group A) Oxy)-p-vinylbenzene, [2-(3-oxetanyl)ethoxy]-p-vinylbenzene, (2-oxetanylmethoxy)-p- Vinylbenzene and [2-(2-oxetanyl)ethoxy]-p-vinylbenzene; and (oxetanylalkyl)vinyl ether, such as (3-oxocyclo) Butyrylmethyl)vinyl ether, [2-(3-oxetanyl)ethyl]vinyl ether, (2-oxetanylmethyl)vinyl ether and [2-( 2-oxetanyl)ethyl]vinyl ether can also be used as the oxetane unsaturated compound.

In the copolymer (B1), the unsaturated compound (b3-1) may be used alone or in two More or more blending is used.

Meanwhile, illustrative examples of the unsaturated compound (b3-2) include tetrahydrofuran ester of (meth)acrylic acid such as tetrahydrofuran-2-(meth)acrylate and tetrahydrofuran-3-(meth)acrylate; Acetylene-containing tetrahydrofurfuryl esters such as tetrahydrofurfuryl (meth)acrylate, 3-tetrahydrofurfuryl (meth)acrylate, 2-(tetrahydrofurfuryloxy)ethyl (meth)acrylate And 2-(3-tetrahydrofurfuryloxy)ethyl (meth)acrylate; 2-(methyl)propenyloxypropionic acid containing tetrahydroindenyl ester, such as 2-(methyl) propylene oxime Tetrahydrofurfuryl propionate, 3-tetrahydrofurfuryl 2-(methyl) propylene oxypropionate, 2-(tetrahydroindenyloxy) ethyl 2-(methyl) propylene oxypropionate and 2 2-(3-tetrahydrofurfuryloxy)ethyl (meth) propylene oxypropionate; vinyl benzene derivative such as (tetrahydrofuran-2-yl)oxy-p-vinylbenzene, (tetrahydrofuran) Ethyloxy-p-vinylbenzene and 2-(tetrahydrofuran-2-yloxy)ethoxy-p-vinylbenzene; vinyl ethers such as (tetrahydrofuran-2-yl) vinyl ether, (four Hydroquinone) vinyl ether, [2-(tetrahydroindenyloxy) ) Ethyl] vinyl ether and [2- (meth) Bing Xixi oxoethyl] (tetrahydrofurfuryl) succinate.

Among these unsaturated compounds (b3-2), a (meth)acrylic acid-containing tetrahydroindenyl ester and [2-(meth)acryloyloxyethyl](tetrahydroindenyl)succinate are preferred. Tetrahydrofurfuryl (meth)acrylate and [2-(meth)acryloyloxyethyl](tetrahydroindenyl) succinate are particularly preferred.

In the copolymer (B1), the unsaturated compound (b3-2) may be used singly or in combination of two or more.

Further, in the present invention, the unsaturated compound (b3) is not saturated And a compound (hereinafter referred to as "unsaturated compound (b3-3)" can also be used as another unsaturated compound.

Illustrative examples of the unsaturated compound (b3-3) include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p- Chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p- Vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; hydrazine, such as hydrazine and 1-methyl巨; a macromonomer having a (meth) acrylonitrile group at one end of a polymer molecular chain (hereinafter referred to as "macromonomer"), such as polystyrene, poly(methyl) methacrylate, poly(A) N-butyl acrylate and polyoxyalkylene; unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylate Propyl ester, (meth) propylene acid n-butyl ester, isobutyl (meth)acrylate, second butyl (meth)acrylate, (meth) propylene Third butyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( 3-hydroxybutyl methacrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) ) 2-ethylhexyl acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, (meth) acrylate Ester, (meth) acrylate, tricyclo [5.2.1.0 ^2.6] decan-8-acrylate, (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate and glycerol (meth) acrylate; unsaturated carboxylic acids Aminoalkyl esters such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, (methyl) 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth)acrylate and 3-dimethylaminopropyl (meth)acrylate; glycidyl ester of unsaturated carboxylic acid such as (methyl) Glycidyl acrylate; vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzylate; other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and olefin Propyl glycidyl ether; vinyl cyanide compounds such as (meth)acrylonitrile, α -chloroacrylonitrile and vinylidene cyanide; and unsaturated decylamines such as (meth) acrylamide, α -chloropropene Indoleamine and N-2-hydroxyethyl(meth)acrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene and isoprene Sulfonic acid

Among these unsaturated compounds (b3-3), styrene, macromonomer, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (methyl) Benzyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate Ester, (meth) acrylate, tricyclo [5.2.1.0 ^2.6] dec-8 acrylate and glycerol mono (meth) acrylate is preferred. Among the macromonomers, polystyrene macromonomers and poly(methyl) methacrylate macromonomers are particularly preferred.

In the copolymer (B1), the unsaturated compound (b3-3) may be used singly or in combination of two or more.

In the present invention, when the copolymer (B1) is a copolymer obtained by polymerizing a polymerizable mixture containing the unsaturated compound (b3) (hereinafter referred to as "copolymer (B1-1)", copolymerization The substance (B1-1) can be used in any of the following forms, that is, [I] wherein an unsaturated compound containing the unsaturated compound (b1), (b2) and (b3-1) and optionally used is used. The copolymer (B1-1) obtained by polymerizing the polymerizable mixture of (b3-3) is in the form of a component of an alkali-soluble resin, [II] wherein the unsaturated compound (b1), (b2) and the unsaturated compound are used. a copolymer (B1-1) obtained by polymerizing (b3-2) and optionally a polymerizable mixture of the unsaturated compound (b3-3) as a component of an alkali-soluble resin, [III] wherein A copolymer obtained by polymerizing a polymerizable mixture containing an unsaturated compound (b1), (b2), (b3-1) and (b3-2) and optionally an unsaturated compound (b3-3) (B1- 1) a form of a component as an alkali-soluble resin, and [IV] wherein a mixture of two or more of the copolymers (B1-1) in the above [I] to [III] is used as Parts of the soluble resin in the form of groups.

In the copolymer (B1), the proportion of the unsaturated compound (b1) to be copolymerized is preferably from 1 to 40% by weight, especially from 5 to 35% by weight, and the proportion of the unsaturated compound (b2) to be copolymerized is preferably It is from 1 to 40% by weight, in particular from 5 to 30% by weight.

Further, when the unsaturated compound (b3) is copolymerized with the unsaturated compound (b1) and the unsaturated compound (b2), the proportion of the unsaturated compound (b3) to be copolymerized is preferably from 1 to 70% by weight, especially 1 The proportion of the unsaturated compound (b3-3) to be copolymerized is preferably from 0 to 70% by weight, more preferably from 1 to 60% by weight, to 40% by weight.

Further, when both the unsaturated compound (b3-1) and the unsaturated compound (b3-2) are copolymerized with the unsaturated compound (b1) and the unsaturated compound (b2), the unsaturated compound to be copolymerized (b3-1) The proportion of the compound is preferably from 1 to 70% by weight, especially from 1 to 40% by weight, and the proportion of the unsaturated compound (b3-2) to be copolymerized is preferably from 1 to 60% by weight, especially from 1 to 40% by weight. %, and the proportion of the unsaturated compound (b3-3) to be copolymerized is preferably from 0 to 70% by weight, more preferably from 1 to 60% by weight.

Further, when the unsaturated compound (b3-1) and the unsaturated compound (b3-2) are copolymerized with the unsaturated compound (b1) and the unsaturated compound (b2), respectively, the unsaturated compound (b3-1) to be copolymerized The proportion is preferably from 1 to 70% by weight, especially from 1 to 40% by weight, and the proportion of the unsaturated compound (b3-3) to be copolymerized is preferably from 0 to 70% by weight, more preferably from 1 to 60% by weight, The proportion of the unsaturated compound (b3-2) to be copolymerized is preferably from 1 to 60% by weight, especially from 1 to 40% by weight, and the proportion of the unsaturated compound (b3-3) to be copolymerized is preferably from 0 to 70. The weight % is more preferably from 1 to 60% by weight.

In the present invention, when the ratio of the unsaturated compound in the copolymer (B1) is within the above range, radiation sensitivity for forming a color layer excellent in sensitivity, substrate adhesion, solvent resistance, and the like can be obtained. Sex Composition.

The copolymer (B1) can be utilized in the presence of a compound represented by the above formula (5) (hereinafter referred to as "polythiol compound") in a suitable solvent, such as a 2,2'-couple. Nitrogen bisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) or 2,2'-azobis(4-methoxy-2,4-dimethyl The valeronitrile is synthesized by polymerizing an unsaturated compound.

As the polythiol compound, a compound represented by the following formula (6) is preferred.

(In the formula (6), Y, R ⁸ and n are as defined in the formula (3).

Illustrative examples of the aforementioned polythiol compound include those derived from mercaptocarboxylic acids (such as thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and 3-mercaptovaleric acid) and polyhydric alcohols (such as ethylene glycol, tetra Ethylene glycol, butanediol, trimethylolpropane, isovaerythritol, diisopentaerythritol, triisotetraol, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid Esters of esters and sorbitol).

Specific examples of preferred polythiol compounds in the present invention include trimethylolpropane tris(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis (3) - mercaptopropionate, diisopentaerythritol hexa(3-mercaptopropionic acid) ester, isoamyl alcohol tetrakis(thioglycolate), 1,4-bis(3-mercaptobutyloxy)butane , pentaerythritol tetrakis(3-mercaptobutyrate) and 1,3,5-gin(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6 (1H, 3H,5H)-trione.

The aforementioned polythiol compounds may be used singly or in combination of two or more.

The polythiol compound is a component which acts as a chain transfer agent during the polymerization of the synthetic copolymer (B1). The present inventors have found that when the polymerization is carried out using a polythiol compound as a chain transfer agent, the unreacted unsaturated compound can be reduced, and the conversion of the unsaturated compound to the polymer by free radical polymerization can be improved, and the conversion can be performed in a short time. The desired copolymer (B1) is synthesized internally. By reducing the unreacted unsaturated compound, the percentage of the pattern film remaining during the shower development and post-baking and the imperfection of the pixel solvent due to the dissolution of the unreacted unsaturated compound can be reduced.

In the polymerization for synthesizing the copolymer (B1), the polythiol compound is preferably used in an amount of from 0.5 to 20 parts by weight, more preferably from 1 to 10 parts by weight, per 100 parts by weight of the total of the unsaturated compound. The radical polymerization initiator is preferably used in an amount of from 0.1 to 50 parts by weight, more preferably from 0.1 to 20 parts by weight, per 100 parts by weight of the total of the unsaturated compound. Further, the polymerization temperature is preferably from 0 to 150 ° C, more preferably from 50 to 120 ° C, and the polymerization time is preferably from 10 minutes to 20 hours, more preferably from 30 minutes to 6 hours.

In the present invention, in the polymerization for synthesizing the copolymer (B1), one or more chain transfer agents other than the polythiol compound, such as a third-dodecyl mercaptan, may be used together with the polythiol compound. And the α -methylstyrene dimer is preferably used in an amount of not more than 90% by weight, more preferably not more than 60% by weight based on all of the chain transfer agents.

In the present invention, the copolymer (B1) has a weight average molecular weight (hereinafter referred to as "Mw") expressed by polystyrene as measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran), preferably 3,000 to 300,000, more preferably good 3,000 to 100,000.

Further, the copolymer (B1) has a number average molecular weight (hereinafter referred to as "Mn") expressed by polystyrene as measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran), preferably 3,000 to 60,000, more preferably 3,000. Up to 25,000.

Further, the ratio of Mw to Mn (Mw/Mn) of the copolymer (B1) is preferably from 1 to 5, more preferably from 1 to 4. A radiation-sensitive composition having excellent developability is obtained by using the copolymer (B1) having the specific Mw or Mn described above. Therefore, a color layer having sharp pattern edges can be formed, and it is difficult to cause residue, scum, film residue, and the like in the unexposed portion or the light shielding layer on the substrate during development.

In the present invention, the copolymer (B1) may be used singly or in combination of two or more.

Further, in the present invention, the copolymer (B1) can be used together with other alkali-soluble resins.

The aforementioned other alkali-soluble resin is not particularly limited and may be any of an addition polymerization resin, a polymerization addition resin, a polycondensation resin, and the like. The addition polymerization resin is preferred.

The above-mentioned other addition polymerization alkali-soluble resin can be, for example, by at least one compound selected from the above unsaturated compound (b1) and at least one compound selected from the aforementioned unsaturated compound (b2) and unsaturated compound (b3-3). The copolymer obtained by carrying out polymerization in the absence of a polythiol compound.

In the present invention, the amount of the alkali-soluble resin is 100 parts by weight. The toner (A) is preferably from 10 to 1,000 parts by weight, more preferably from 20 to 500 parts by weight. For example, when the amount of the alkali-soluble resin is too small, alkali developability may be lowered, or scum or film residue may be generated in the unexposed portion or the light-shielding layer on the substrate. On the other hand, when the equivalent is too large, the concentration of the colorant becomes relatively low, and it may be difficult to achieve the target color density of the film.

Further, the amount of the other alkali-soluble resin is preferably not more than 80% by weight, more preferably not more than 60% by weight based on the total of the alkali-soluble resin. When the amount of the other alkali-soluble resin exceeds 80% by weight, the effects to be achieved by the present invention may be impaired.

-(C) Polyfunctional monomer -

The polyfunctional single system of the present invention comprises monomers having two or more polymerizable unsaturated bonds per molecule.

Illustrative examples of the polyfunctional monomer include alkanediols such as di(meth)acrylates of ethylene glycol and propylene glycol; polyalkylene glycols such as polyethylenes, polypropylenes, di(meth)acrylic acid An ester; a poly(meth) acrylate having three or more hydroxyl groups such as glycerol, trimethylolpropane, pentaerythritol, and diisopentaerythritol, and a modification with a dicarboxylic acid ( Methyl) acrylate; oligo(meth) acrylate of polyester, epoxy resin, urethane resin, alkyd resin, polyoxyn epoxide resin, spiro resin, etc.; hydroxylated at both ends a polymer such as poly-1,3-butadiene having a hydroxyl group at both ends, polyisoprene having a hydroxyl group at both terminals, and polycaprolactone having a hydroxyl group at both terminals Acrylate; and tris[2-(methyl)propenyloxyethyl]phosphate.

Among these polyfunctional monomers, a poly(meth) acrylate having a polyhydric alcohol of three or more hydroxy groups and a poly(meth) acrylate modified with a dicarboxylic acid are preferred, in detail, three Hydroxymethylpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol IV Methacrylate, diisopentyl alcohol pentaacrylate, diisopentyl alcohol penta methacrylate, diisopentyl alcohol hexaacrylate, diisopentyl alcohol hexamethacrylate, the following formula (1II) Compounds shown: And a compound represented by the following formula (IV): . In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and diisopentyl alcohol hexaacrylate are particularly preferred because a color layer having excellent strength and surface smoothness is obtained, and since it is not easy to be on the substrate Scum, film residue, and the like are generated in the unexposed portion and on the light shielding layer.

The aforementioned polyfunctional monomers may be used singly or in combination of two or more.

The amount of the polyfunctional monomer of the present invention is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). When the amount of the polyfunctional monomer is too small, the strength and surface smoothness of the color layer may be lowered, and when the amount is too large, alkali developability It may be lowered, or scum, film residue, and the like may be easily generated in the unexposed portion of the substrate or on the light shielding layer.

Further, in the present invention, a monofunctional monomer having a polymerizable unsaturated bond can be used in combination with a polyfunctional monomer.

The illustrative examples of the aforementioned monofunctional monomer include a compound which is an example of the unsaturated compound (b1), (b2) or (b3) in the alkali-soluble resin (B), N-(methyl)propenylmorphomorpholine. N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and commercially available product M-5600 (trade name of Toagosei Co., Ltd.).

These monofunctional monomers may be used singly or in combination of two or more.

The monofunctional monomer is preferably used in an amount of not more than 90% by weight, more preferably not more than 50% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer. When the amount of the monofunctional monomer is too large, the strength and surface smoothness of the color layer to be obtained may become insufficient.

The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). For example, when the total amount is too small, the strength and surface smoothness of the color layer may be lowered, and when the total amount is too large, the alkali developability may be lowered, or scum, film may be easily generated in the unexposed portion or the light shielding layer on the substrate. Residues and the like.

-(D) Photopolymerization initiator -

The photopolymerization initiator of the present invention is exposed radiation (such as visible light, When ultraviolet radiation, far ultraviolet radiation, electron beam or X-ray is used, a compound which can initiate polymerization of the above-mentioned polyfunctional monomer (C) and optionally a monofunctional monomer is used.

Illustrative examples of such a photopolymerization initiator include an acetophenone compound, a biimidazole compound, a triazine compound, an O-mercaptopurine compound, an onium salt compound, a benzoin compound, a benzophenone compound, and an α-diketone. Compounds, polycyclic guanidine compounds, xanthone compounds, diazo compounds and sulfhydrazine sulfonate compounds. These compounds produce active free radicals and/or active acids upon exposure.

The photopolymerization initiator of the present invention is preferably at least one selected from the group consisting of an acetone compound, a biimidazole compound, a triazine compound, and an O-indenyl hydrazine compound.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more.

In the present invention, the photopolymerization initiator is preferably used in an amount of from 0.01 to 120 parts by weight, more preferably from 1 to 100 parts by weight based on the total of the polyfunctional monomer (C) and the monofunctional monomer. 100 parts by weight. When the amount of the photopolymerization initiator is too small, curing by exposure is insufficient, and it may become difficult to obtain a color filter having a color layer pattern arranged according to a specific configuration, and when the amount is too large, The formed colored layer may be detached from the substrate during development.

Specific examples of the ethoxylated benzene compound in the preferred photopolymerization initiator of the present invention include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine Base-1-(4-morpholinylphenyl)butan-1-one, 1-hydroxycyclohexyl. Phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one and 1,2-octanedione.

Among these ethoxylated benzene compounds, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine The base-1-(4-morpholinylphenyl)butan-1-one and 1,2-octanedione are particularly preferred.

The aforementioned ethoxylated benzene compound may be used singly or in combination of two or more.

In the present invention, when an ethoxylated benzene compound is used as a photopolymerization initiator, the acetal benzene compound is used in an amount of 100 parts by weight based on the total amount of the polyfunctional monomer (C) and the monofunctional monomer. It is preferably from 0.01 to 80 parts by weight, more preferably from 1 to 70 parts by weight, particularly preferably from 1 to 60 parts by weight. When the amount of the acetal benzene compound is too small, insufficient curing by exposure makes it difficult to obtain a color filter having a color layer pattern arranged according to a specific configuration, and when the amount is too large, The formed colored layer may be detached from the substrate during development.

Further, specific examples of the aforementioned biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbylphenyl)-1, 2'-Biimidazole, 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-dichlorobenzene -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked Imidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2, 4,6-tribromophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole.

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 and 2,2'-bis(2,4,6-trichlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl Base-1,2'-biimidazole is preferred.

These biimidazole compounds have excellent solubility in a solvent, do not generate foreign matter such as insolubles and precipitates, are highly sensitive, allow the curing reaction to proceed sufficiently under low-energy exposure, and do not cause in an unexposed portion. The curing reaction, therefore, the film after exposure is clearly distinguished as a solidified portion which is insoluble in the developer and an uncured portion which has high solubility in the developer, and can be formed to have a pattern having no undercut color layer pattern arranged according to a specific configuration. Clearness color filter.

The aforementioned biimidazole compound may be used singly or in combination of two or more.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, the amount of the biimidazole compound is preferably 100 parts by weight based on the total amount of the polyfunctional monomer (C) and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the biimidazole compound is too small, insufficient curing by exposure makes it difficult to obtain a color filter having a color layer pattern arranged according to a specific configuration, and when the amount is too large, the formed The colored layer may be detached from the substrate, or the surface of the colored layer may be roughened when it is easy to develop.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, It is preferably used in combination with the following hydrogen donor because the sensitivity can be further improved.

The "hydrogen donor" means a compound which can provide a radical in which a hydrogen atom is supplied from the biimidazole compound upon exposure.

As the hydrogen donor of the present invention, preferred are thiol compounds, amine compounds and the like as defined hereinafter.

The above thiol compound comprises a compound having a benzene ring or a heterocyclic ring as a mother nucleus and one or more, preferably one to three, more preferably one or two thiol groups directly bonded to the mother nucleus (hereinafter referred to as "sulfur Alcohol hydrogen donor").

The above amine compound is a compound having a benzene ring or a hetero ring as a mother nucleus and one or more, preferably one to three, more preferably one or two amine groups directly bonded to the mother nucleus (hereinafter referred to as "amine" Hydrogen donor").

In addition, such hydrogen donors may also have a mercapto group and an amine group.

These hydrogen donors are further described below.

The thiol hydrogen donor may have at least one benzene ring or heterocyclic ring and may have both a benzene ring and a heterocyclic ring which, when containing two or more such rings, may form a fused ring.

Further, when the thiol hydrogen donor has two or more mercapto groups, one or more remaining mercapto groups may be substituted by an alkyl group, as long as at least one free mercapto group is retained, at least one of the other mercapto groups may be via an alkyl group or an aralkyl group. Substituting a aryl group or an aryl group, and as long as at least one free thiol group is retained, the thiol hydrogen donor may have a structural unit in which two sulfur atoms are bonded via a divalent organic group (such as an alkylene group) or two sulfur atoms therein A structural unit bonded in the form of a disulfide.

Further, in the thiol hydrogen donor, the position other than the thiol group may be substituted by a carboxyl group, an alkoxycarbyl group, a substituted alkoxycarbonyl group, or a phenoxy group. Carbon based, substituted phenoxy carbon group, nitrile group or the like.

Specific examples of such a thiol hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole And 2-mercapto-2,5-dimethylaminopyridine.

Among these thiol hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferred, and 2-mercaptobenzothiazole is particularly preferred.

In another aspect, the amine hydrogen donor can have at least one benzene or heterocyclic ring or both a benzene ring and a heterocyclic ring which, when containing two or more such rings, can form a fused ring.

Further, in the amine hydrogen donor, one or more amine groups may be substituted by an alkyl group or a substituted alkyl group, and the position other than the amine group may be substituted by a carboxyl group, an alkoxy carbon group, a Substituted alkoxycarbonyl, phenoxycarbonyl, substituted phenoxycarbyl, nitrile or the like.

Specific examples of such amine hydrogen donors include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-di Ethylaminoethenylbenzene, 4-dimethylaminopropionylbenzene, ethyl-4-dimethylaminobenzyl ester, 4-dimethylaminobenzyl acid and 4-dimethyl Aminobenzonitrile.

Among these amine hydrogen donors, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone are preferred, and 4, 4 '-Bis(diethylamino)benzophenone is particularly preferred.

The amine hydrogen donor has an effect as a sensitizer, even when used in combination with a radical generating agent other than the biimidazole compound.

In the present invention, the hydrogen donor may be used singly or in combination of two or more. Preferably, at least one thiol hydrogen donor and at least one amine hydrogen donor are used The composition is because the formed color layer is not easily peeled off from the substrate during development and the color layer has high strength and sensitivity.

Specific examples of the composition of the thiol hydrogen donor and the 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 and 2-mercaptobenzophenone Azole / 4,4'-bis(diethylamino)benzophenone. More preferred compositions are 2-mercaptobenzothiazole/4,4'-bis(diethylamino)benzophenone and 2-mercaptobenzoxazole/4,4'-bis(diethylamine) Base) benzophenone. A particularly preferred composition is 2-mercaptobenzothiazole/4,4'-bis(diethylamino)benzophenone.

In the composition of the thiol hydrogen donor and the amine hydrogen donor, the weight of the thiol hydrogen donor relative to the amine hydrogen donor is preferably from 1:1 to 1:4, more preferably from 1:1 to 1: 3.

In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the hydrogen donor is preferably used in an amount of 100 parts by weight of the polyfunctional monomer (C) and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the hydrogen donor is too small, the effect of improving the sensitivity is liable to be lowered, and when the amount is too large, the formed color layer may be easily peeled off from the substrate at the time of development.

Further, specific examples of the aforementioned triazine compound include a triazine compound having a halomethyl group such as 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-double (trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2 -[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethyl Amino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl ]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2- (4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethane) Base)-s-triazine.

Among these triazine compounds, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine is particularly preferred.

The aforementioned triazine compounds may be used singly or in combination of two or more.

In the present invention, when the triazine compound is used as the photopolymerization initiator, the amount of the triazine compound is preferably 100 parts by weight based on the total amount of the polyfunctional monomer (C) and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the triazine compound is too small, insufficient curing by exposure makes it difficult to obtain a color filter having a color layer pattern arranged according to a specific configuration, and when the amount is too large, the formed color The layer may fall off the substrate during development.

Further, specific examples of the aforementioned O-indenyl ruthenium compound include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzidine), 1- [4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzylhydrazine), 1-[4-(benzylidene)phenyl]-octane-1 ,2-dione 2-(O-benzylhydrazine), 1-[9-ethyl-6-(2-methylbenzylindenyl)-9H-indazol-3-yl]ethanone 1-(O -acetamidine), 1-[9-ethyl-6-(3-methylbenzyl)-9H-indazol-3-yl]ethanone 1-(O-acetamidine), 1-[9-ethyl-6-benzylindol-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-( 2-methyl-4-tetrahydrofuranbenzylbenzyl)-9.H.-carbazol-3-yl]-1-(O-acetyl), ethyl ketone-1-[9-ethyl-6- (2-methyl-4-tetrahydropiperidinylbenzyl)-9.H.-carbazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-B -6-(2-methyl-5-tetrahydrofuranbenzylbenzyl)-9.H.-oxazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9- Ethyl-6-(2-methyl-5-tetrahydropiperidinylbenzyl)-9.H.-carbazol-3-yl]-1-(O-acetyl), ethyl ketone-1 -[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzylindenyl}-9.H.-carbazole-3 -yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzyl)-9.H.- Oxazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzyl) )-9.H.-carbazol-3-yl]-1-(O- Ethyl hydrazide), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzyl)-9.H.-carbazol-3-yl]-1 -(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzyl)-.H.-carbazole -3-yl-]-1-(O-acetamidine) and ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3 - Dioxolyl)methoxybenzylhydrazino}-9.H.-oxazol-3-yl]-1-(O-acetamidine).

Among these O-mercaptopurine compounds, 1-[4-(phenylthio)phenyl]- Octane-1,2-dione 2-(O-benzidine), 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]ethanone 1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzyl)-9.H.-carbazole-3 -yl]-1-(O-acetamidine) and ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo) Pentocyclo)methoxybenzylamino}-9.H.-oxazol-3-yl]-1-(O-acetyl) is particularly preferred.

The aforementioned O-indenyl hydrazine compounds may be used singly or in combination of two or more.

In the present invention, when an O-indenyl ruthenium compound is used as a photopolymerization initiator, the O-indenyl ruthenium compound is used in an amount of 100 parts by weight of the polyfunctional monomer (C) and the monofunctional monomer. The gauge is preferably from 0.01 to 80 parts by weight, more preferably from 1 to 70 parts by weight, particularly preferably from 1 to 60 parts by weight. When the amount of the O-acetamidine compound is too small, insufficient curing by exposure makes it difficult to obtain a color filter having a color layer pattern arranged according to a specific configuration, and when the amount is too large, The formed color layer may be easily peeled off from the substrate during development.

-additive-

The radiation-sensitive composition used to form the colored layer of the present invention may optionally contain various additives.

Illustrative examples of the aforementioned additives include organic acids and organic amine based compounds (excluding the aforementioned hydrogen donors), curing agents, and curing assistants.

The above organic acid and organic amine based compound are components for producing an effect of further improving the solubility of the radiation-sensitive composition in an alkali developer and further suppressing the effect of residual insoluble matter after development.

As the above organic acid, an aliphatic carboxylic acid having one or more carboxyl groups in the molecule or a carboxylic acid having a phenyl group is preferred.

Specific examples of the aforementioned aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; dicarboxylic acids such as Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, branic acid, methylmalonic acid, ethylmalonic acid, two Methylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, isaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; and tricarboxylic acid Acids such as glycerol, aconitic acid and camphoric acid.

Further, illustrative examples of the aforementioned phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to a phenyl group and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain.

Specific examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzylic acid, toluic acid, lauric acid, benzotricarboxylic acid, and dimethylbenzyl acid; aromatic dicarboxylic acids such as phthalic acid, Isophthalic acid and terephthalic acid; aromatic polycarboxylic acids having 3 or more carboxyl groups, such as trimellitic acid, trimellitic acid, pyromellitic acid and pyromellitic acid; and phenylacetic acid, hydrogenated Oleic acid, hydrogenated cinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamic acid, coumaric acid and umbrella acid.

Among these organic acids, aliphatic dicarboxylic acids are preferred, and in terms of alkali solubility, Malonic acid, adipic acid, isaconic acid, citraconic acid, anti-butene, from the viewpoints of the solubility in the solvent described below and the prevention of scum and film residues in the unexposed portion of the substrate or on the light shielding layer Diacids, mesaconic acids, and the like are particularly preferred aliphatic carboxylic acids. Further, as the phenyl group-containing carboxylic acid, an aromatic dicarboxylic acid is preferred, and a phthalic acid is particularly preferred.

The aforementioned organic acids may be used singly or in combination of two or more.

The amount of the organic acid is preferably not more than 15% by weight, more preferably not more than 10% by weight, based on the total solid content of the radiation-sensitive composition. When the amount of the organic acid is too large, the adhesion of the formed color layer to the substrate may be lowered.

Further, as the above organic amine-based compound, an aliphatic amine or a phenyl group-containing amine having one or more amine groups in the molecule is preferred.

Specific examples of the aforementioned aliphatic amines include mono(cyclo)alkylamines such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, N-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methyl Cyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, and 4-ethylcyclohexylamine; di(cyclo)alkane Base amines, such as methyl ethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, di-isopropylamine, di-n-butyl Amine, di-isobutylamine, di-secondbutylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and Dicyclohexylamine; tri(cyclo)alkylamines such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine , diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri- Isobutylamine, tri-t-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyl Dicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine; mono(cyclo)alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol Alcohol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol and 4-amino-1-cyclohexanol; di(cyclo)alkanolamine , such as diethanolamine, di-n-propanolamine, di-isopropanolamine, di-n-butanolamine, di-isobutanolamine, di-n-pentanolamine, di-n-hexanolamine, and di(4- Cyclohexanol)amine; tri(cyclo)alkanolamines, such as triethanolamine, tri-n-propanolamine, tri-isopropanolamine, tri-n-butanolamine, tri-isobutanolamine, tri-n-pentane Alcoholamine, tri-n-hexanolamine and tris(4-cyclohexanol)amine; amine (cyclo)alkanediol, such as 3-amino-1,2 -propane diol, 2-amino-1,3-propane diol, 4-amino-1,2-butane diol, 4-amino-1,3-butane diol, 4-amino group -1,2·cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol,

3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol; amine-containing Base naphthenic acid methanol, such as 1-aminocyclopentane methanol, 4-aminocyclopentane methanol, 1-aminocyclohexane methanol, 4-aminocyclohexane methanol, 4-dimethylamino group Cyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol, and 4-diethylaminocyclohexane methanol; and an aminocarboxylic acid such as β- Alanine 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-amino group Valeric acid, 6-aminohexanoic acid, 1-Aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid.

Further, illustrative examples of the aforementioned phenyl group-containing amine include compounds in which an amine group is directly bonded to a phenyl group and a compound in which an amine group is bonded to a phenyl group via a carbon chain.

Specific examples of the phenyl-containing amine include aromatic amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4 -Isopropylaniline, 4-n-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline And 4-methyl-N,N-dimethylaniline; aminobenzyl alcohol, such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethyl Aminobenzyl alcohol and 4-diethylaminobenzyl alcohol; and aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol And 4-diethylaminophenol.

Among these organic amine-based compounds, as an aliphatic amine, in terms of solubility in a solvent and prevention of formation of dross and film residue on an unexposed portion of a substrate or on a light-shielding layer The cycloalkanolamine and the amine (cyclo)alkanediol are preferred, and the 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1 2-propanediol, 2-amino-1,3-propanediol and 4-amino-1,2-butanediol are particularly preferred. Further, as the phenyl group-containing amine, an aminophenol is preferred, and 2-aminophenol, 3-aminophenol and 4-aminophenol are particularly preferred.

The amount of the organic amine group is preferably not more than 15% by weight, more preferably not more than 10% by weight, based on the total solids of the radiation-sensitive composition. Organic amine When the amount of the base compound is too large, the adhesion of the formed color layer to the substrate may be lowered.

The curing agent is a component which cures the alkali-soluble resin (B) by reacting with a carboxyl group and/or an oxetane ring in the alkali-soluble resin (B).

Illustrative examples of such curing agents include epoxy compounds and oxetane compounds.

The epoxy compound is preferably a polyfunctional epoxy compound. Specific examples thereof 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 type epoxy resin; Epoxy resin, such as alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester resin, glycidylamine resin and epoxidized oil; brominated derivatives of such epoxy resins, and epoxidized dibutyl An olefin (co)polymer, an epoxidized isoprene (co)polymer, a (co)polymer of a glycidyl group-containing unsaturated compound, and a triglycidyl isocyanurate.

Further, an epoxy group-containing unsaturated compound is also desirable as the aforementioned epoxy compound. Specific examples thereof include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, o-vinylbenzyl glycidol. An ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.

On the other hand, the oxetane compound is preferably a polyfunctional oxetane compound. Specific examples thereof include low molecular weight compounds such as dioxetane carbonate, dioxetane adipate, p-benzene. Dioxetane dicarboxylate, dioxetane p-terephthalate and dioxetane 1,4-cyclohexanedicarboxylate, and high molecular weight compounds such as oxygen-containing heterocycles a (co)polymer of butane etherified phenolic resin and an unsaturated compound having an oxetane ring structure (excluding copolymer (B1)). The copolymer (B1) having an oxetane ring structure is a component having an effect as a curing agent.

Further, a compound having both an oxetane ring structure and an unsaturated double bond is also an ideal oxetane compound. Specific examples thereof include compounds exemplified as the aforementioned unsaturated compound (b3-1).

These curing agents may be used singly or in combination of two or more.

The curing agent is preferably used in an amount of not more than 30% by weight, more preferably not more than 20% by weight, based on the total of the solids of the radiation-sensitive composition. When the amount of the curing agent is too large, the storage stability of the radiation-sensitive composition to be produced may be lowered.

The curing aid is a component which accelerates the curing reaction of the curing agent by opening the epoxy group and/or the oxetane ring of the curing agent.

Illustrative examples of such curing assistants include polycarboxylic acids, polycarboxylic anhydrides, and amine based compounds.

Specific examples of the aforementioned polycarboxylic acid include compounds as exemplified in the foregoing organic acids for compounds having two or more carboxyl groups. Specific examples of the aforementioned amine-based compound include compounds as exemplified for the aforementioned organic amine-based compound.

Further, specific examples of the aforementioned polycarboxylic acid anhydride include aromatic polycarboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3',4,4'-diphenylmethanonetetracarboxylic acid. A dianhydride; an aliphatic polycarboxylic acid anhydride such as isaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, propylene tricarboxylic anhydride, maleic anhydride, and 1,2,3,4-butane IV Anic anhydride; an alicyclic polycarboxylic anhydride such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentane tricarboxylic anhydride, 1,2,4- Cyclohexanetricarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-positive Alkene-2,3-dicarboxylic anhydride and methic anhydride; carboxylic acid anhydride containing an ester group, such as ethylene glycol dibenzoic acid anhydride and glycerol benzene tricarboxylic acid anhydride; and commercially available epoxy resin curing agent The trade name is ADEKA HARDENER EH-700 (product of ADEKA CORPORATION), RIKACID HH (product of New Japan Chemical Co., Ltd.), and MH-700 (product of New Japan Chemical Co., Ltd.).

The aforementioned curing assistants may be used singly or in combination of two or more.

The amount of the curing assistant is preferably not more than 15% by weight, more preferably not more than 10% by weight, based on the total of the solids of the radiation-sensitive composition. When the amount of the curing assistant is too large, the storage stability of the radiation-sensitive composition to be produced may be lowered or the formed colored layer may be easily peeled off from the substrate upon development.

Further, illustrative examples of the additive other than the foregoing additives include a dispersing aid such as a blue pigment derivative or a yellow pigment derivative such as a copper phthalocyanine derivative; a filler such as glass or alumina; a polymer compound , such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or poly(fluoroalkyl acrylate); nonionic, cationic or anionic surfactant; adhesion promoter, such as vinyl trimethoxy decane, Vinyl triethoxy decane, vinyl tris(2-methoxyethoxy)decane, N-(2-amino group Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane , 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane; An oxidizing agent such as 2,2'-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; an ultraviolet light absorber such as 2-(3- Tributyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; a cohesion inhibitor such as sodium polyacrylate; and a thermal radical generating agent such as 1,1'-Azobis(cyclohexane-1-carbonitrile) or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

- solvent -

The radiation-sensitive composition for forming a color layer of the present invention contains the above components (A) to (D) as essential components and optionally the aforementioned additives, and is usually mixed with a solvent to prepare a liquid composition.

As the solvent, any suitable solvent may be selected and used as long as the solvent disperses or dissolves the components (A) to (D) and the component of the composition constituting the radiation-sensitive composition without reacting with the components, and Have appropriate volatility.

Illustrative examples of such solvents include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol single - n-butyl ether, diethylene glycol monomethyl ether, double ethylene Alcohol monoethyl ether, bisethylene glycol mono-n-propyl ether, bisethylene glycol mono-n-butyl ether, ginseng ethylene glycol monomethyl ether, ginseng ethylene glycol monoethyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol single - n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly) alkanediol monoalkyl ether acetate, such as ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl ether acetate, bisethylene glycol monomethyl ether acetate, bisethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Ethers such as diethylene glycol dimethyl ether, bisethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone And 3-heptanone; alkyl lactate such as methyl lactate and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate , isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoacetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; and decylamine or Amidoxime compounds such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidinone.

From the viewpoints of solubility, pigment dispersibility, coatability, and the like, among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl group Ether acetate, propylene glycol monoethyl ether acetate, bisethylene glycol dimethyl ether, bisethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate Ester, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate are preferred. The foregoing solvents may be used singly or in combination of two or more.

In addition, high boiling solvents such as benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl b Acid ester, ethyl benzyl ester, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate or ethylene glycol monophenyl ether acetate, It can be used together with the aforementioned solvent.

These high boiling solvents may be used singly or in combination of two or more.

Although not particularly limited, in view of the coatability, stability, and the like of the resulting radiation-sensitive composition, it is desirable that the amount of the solvent be used to determine all groups of the radiation-sensitive composition to be prepared except solvent. The total concentration of the parts becomes preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight.

Color filter

The color filter of the present invention has a color layer formed from the radiation-sensitive composition of the present invention for forming a colored layer.

A method of forming a color layer in the color filter of the present invention is described below.

First, a light shielding layer is formed on the surface of the substrate as appropriate to define a portion for forming a pixel. A liquid radiation-sensitive composition (which contains, for example, a red pigment dispersed therein) is applied to the substrate, and pre-baked to evaporate the solvent to form a coating film.

The coating film is then exposed to radiation via a reticle, developed with an alkali developing solution, dissolved and removed from the unexposed portions of the coating film, and post-baked to form a red pixel array having a predetermined pattern.

Thereafter, the liquid radiation sensitive composition containing the green or blue pigment dispersed therein is separately applied, pre-baked, exposed, developed, and post-baked to form a green pixel array and blue on the same substrate in sequence. A pixel array is obtained, and a color filter in which red, green, and blue pixel arrays are arranged on the substrate is obtained. However, in the present invention, the order in which the three color pixels are formed is not limited to the foregoing.

Further, a black matrix may be formed using, for example, a liquid radiation-sensitive composition in which a black pigment is dispersed, in such a manner as to form the aforementioned pixels.

Illustrative examples of substrates used to form pixels and/or black matrices include glass, ruthenium, polycarbonate, polyester, aromatic polyamines, polyamido-imines, and polyimines.

In addition, such substrates may optionally be subjected to suitable pre-treatments such as chemical treatment, plasma treatment, ion plating, sputtering, gas phase reaction or vacuum deposition using a decane coupling agent or the like.

When the liquid radiation-sensitive composition is applied to the substrate, any suitable coating method such as spray coating, roll coating, spin coating, flat Nozzle coating, rod coating or inkjet coating. Excellent spin coating method and flat nozzle coating method.

The thickness of the coating film after drying is preferably from 0.1 to 10 μm, more preferably from 0.2 to 8.0 μm, particularly preferably from 0.2 to 6.0 μm.

As the radiation for forming the color layer, for example, visible light, ultraviolet radiation, far ultraviolet radiation, electron beam, X-ray or the like can be used. Radiation having a wavelength of 190 to 450 nm is preferred.

The exposure dose of the radiation is preferably from 10 to 10,000 J/m ² .

Further, as the alkali developer, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7- is preferred. An aqueous solution of undecene or 1,5-diazabicyclo-[4.3.0]-5-decene.

It is also possible to add an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to the aforementioned alkali developer. The coating film is usually washed with water after development with an alkali developer.

As the developing method, for example, spray-type development, spray development, immersion development, smelting development, or the like can be employed. Development is preferably carried out at room temperature for 5 to 300 seconds.

The resulting color filter of the present invention can be used extremely effectively for, for example, a transmissive or reflective type color liquid crystal display element, a color camera tube device, a color sensor, or 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. Further, as a form of the color liquid crystal display element of the present invention, a pixel and/or a black matrix may be formed on the thin film transistor substrate array by using the radiation sensitive composition of the present invention for forming a color layer as described above. A color liquid crystal display element having particularly excellent characteristics.

Example

The invention is further described below with reference to examples. However, the invention should not be limited to the following examples.

Synthesis of copolymer (B1) Synthesis Example 1

Adding 3 parts by weight of 2,2'-azobisisobutyronitrile as a radical polymerization initiator and 200 parts by weight of propylene glycol monomethyl ether as a solvent in a flask equipped with a cooling tube and a stirrer Acid ester. Thereafter, 25 parts by weight of N-phenyl maleimide, 15 parts by weight of styrene, 30 parts by weight of methacrylic acid, and 10 parts by weight of n-butyl methacrylate as a polymerizable unsaturated compound are added. Ester and 20 parts by weight of benzyl methacrylate and 7 parts by weight of isoamyl alcohol tetrakis(3-mercaptopropionate) (product of SAKAI CHEMICAL INDUSTRY CO., LTD.) as a polythiol compound, inside the flask Ventilation with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 ° C under gentle agitation, and polymerization was carried out at this temperature for 5 hours to obtain a solution of the copolymer (B1) (solid concentration = 35.5 wt%, polymerization conversion ratio: 100 wt%). This copolymer (B1) is called "alkali-soluble resin" B-1)".

The polymerization conversion ratio was calculated from the actual feed weight of the component subjected to radical polymerization and the solid concentration (% by weight) of the obtained copolymer solution according to the following formula. In order to determine the solid concentration, the weight of the obtained copolymer solution before and after heating was measured, and the solution was weighed in an aluminum pan and heated on a hot plate at 180 ° C for 2 hours, and the solid concentration was calculated by (weight after heating × 100 / weight before heating) . Polymerization conversion ratio (% by weight) = concentration (% by weight) of the copolymer solution after polymerization × total weight of the actual feed of all components / total weight of the actual feed of the components other than the solvent.

Synthesis Example 2

A copolymer (B1) solution (solid concentration = 35.5 wt%, polymerization conversion: 100 wt%) was obtained in the same manner as in Synthesis Example 1, except that the polymerizable unsaturated compound was changed to 25 parts by weight of N-phenyl group. Maleimide, 15 parts by weight of styrene, 15 parts by weight of methacrylic acid, 20 parts by weight of n-butyl methacrylate and 25 parts by weight of 3-(methacryloxymethyl) 3-ethyloxetane. This copolymer (B1) is called "alkali-soluble resin (B-2)".

Synthesis Example 3

A copolymer (B1) solution (solid concentration = 35.5 wt%, polymerization conversion: 100 wt%) was obtained in the same manner as in Synthesis Example 1, except that the polymerizable unsaturated compound was changed to 25 parts by weight of N-phenyl group. Maleimide, 15 parts by weight of styrene, 15 parts by weight of methacrylic acid, 20 parts by weight of n-butyl methacrylate and 25 parts by weight of tetrahydrofurfuryl methacrylate. This copolymer (B1) is called "alkali-soluble resin (B-3)".

Synthesis Example 4

A copolymer (B1) solution (solid concentration = 35.5 wt%, polymerization conversion: 100 wt%) was obtained in the same manner as in Synthesis Example 1, except that the polymerizable unsaturated compound was changed to 25 parts by weight of N-phenyl group. Maleimide, 15 parts by weight of styrene, 15 parts by weight of methacrylic acid, 20 parts by weight of n-butyl methacrylate, 15 parts by weight of 3-(methacryloxymethyl) 3-Ethyloxetane and 10 parts by weight of tetrahydrofurfuryl methacrylate. This copolymer (B1) is called "alkali-soluble resin (B-4)".

Synthesis Example 5

A copolymer (B1) solution (solid concentration = 35.5 wt%, polymerization conversion ratio: 100 wt%) was obtained in the same manner as in Synthesis Example 1, except that the polythiol compound was changed to 7 parts by weight of tetraethylene glycol (ethylene glycol). Bis(3-mercaptopropionate) (product of SAKAI CHEMICAL INDUSTRY CO., LTD.). This copolymer (B1) is called "alkali-soluble resin (B-5)".

Synthesis Example 6

A copolymer (B1) solution was obtained in the same manner as in Synthesis Example 1 (solid concentration = 35.5 wt%, polymerization conversion ratio: 100 wt%), and the difference was The polythiol compound was changed to 7 parts by weight of diisopentyl alcohol bis(3-mercaptopropionate) (product of SAKAI CHEMICAL INDUSTRY CO., LTD.). This copolymer (B1) is called "alkali-soluble resin (B-6)".

Synthesis Example 7

A copolymer (B1) solution (solid concentration = 35.4% by weight, polymerization conversion: 99.8% by weight) was obtained in the same manner as in Synthesis Example 1, except that the polythiol compound was changed to 7 parts by weight of 1,4-double ( 3-mercaptobutyloxy)butane (product of Showa Denko KK). This copolymer (B1) is called "alkali-soluble resin (B-7)".

Synthesis Example 8

A copolymer (B1) solution (solid concentration = 35.3 wt%, polymerization conversion: 99.5% by weight) was obtained in the same manner as in Synthesis Example 1, except that the polythiol compound was changed to 7 parts by weight of isopentaerythrin IV ( 3-mercaptobutyrate) (product of Showa Denko KK). This copolymer (B1) is called "alkali-soluble resin (B-8)".

Synthesis Example 9

A copolymer (B1) solution (solid concentration = 35.4% by weight, polymerization conversion ratio: 99.8% by weight) was obtained in the same manner as in Synthesis Example 2, except that the polythiol compound was changed to 7 parts by weight, 1, 3, 5- Ginseng (3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (product of Showa Denko KK). This copolymer (B1) is called "alkali solubility" Resin (B-9)".

Synthesis of control composition Synthesis Example 10

A copolymer solution (solid concentration = 34.9% by weight, polymerization conversion: 98.4% by weight) was obtained in the same manner as in Synthesis Example 1, except that the polymerizable unsaturated compound was changed to 15 parts by weight of methacrylic acid and 15 parts by weight. A number of styrene and 70 parts by weight of benzyl methacrylate. This copolymer is referred to as "alkali-soluble resin (B-10)".

Synthesis Example 11

A copolymer solution (solid concentration == 34.0% by weight, polymerization conversion ratio: 95.8 wt%) was obtained in the same manner as in Synthesis Example 1, except that 7 parts by weight of a third-dodecyl mercaptan was used in place of the difference. Pentaerythritol tetrakis(3-mercaptopropionic acid). This copolymer is referred to as "alkali-soluble resin (B-11)".

Synthesis Example 12

A copolymer solution (solid concentration == 31.0% by weight, polymerization conversion ratio: 87.4% by weight) was obtained in the same manner as in Synthesis Example 1, except that 7 parts by weight of 2,4-diphenyl-4-methyl group was used. 1-pentene (product of NOF CORPORATION) replaces isopentanol tetrakis(3-mercaptopropionate). This copolymer is referred to as "alkali-soluble resin (B-12)".

Comparison of polymerization rates Synthesis Example 13

A copolymer (B-1) solution was obtained in the same manner as in Synthesis Example 1, except that the polymerizable unsaturated compound was changed to 15 parts by weight of N-phenyl maleimide, and 8 parts by weight of styrene. 15 parts by weight of methacrylic acid, 15 parts by weight of 2-hydroxyethyl methacrylate, 28 parts by weight of 2-ethylhexyl methacrylate and 19 parts by weight of benzyl methacrylate. In this case, after the temperature of the reaction solution was raised to 80 ° C, a sample of the reaction solution was taken every hour, and the solid concentration of each sample was measured to trace the polymerization conversion ratio. The results are shown in Table 1. The copolymer obtained by polymerizing for 2 hours after the temperature of the reaction solution is raised to 80 ° C is called "alkali-soluble resin (B-13)", and the copolymer obtained by polymerizing for 5 hours after the temperature of the reaction solution is raised to 80 ° C is called "alkali solubility." Resin (B-14)". The alkali-soluble resin (B-14) has a Mw of 7,000 and an Mn of 4,400.

Synthesis Example 14

The polymerization conversion ratio was followed in the same manner as in Synthesis Example 13 and a copolymer solution was obtained, except that 2,4-diphenyl-4-methyl-1-pentene was used instead of isopentaerythritol tetrakis(3-mercaptopropylidene). Acid ester). The copolymer obtained by polymerizing for 2 hours after the temperature of the reaction solution is raised to 80 ° C is called "alkali-soluble resin (B-15)", and the copolymer obtained by polymerizing for 5 hours after the temperature of the reaction solution is raised to 80 ° C is called "alkali solubility." Resin (B-16)". The alkali-soluble resin (B-16) has a Mw of 9,000 and an Mn of 4,300.

Preparation of pigment dispersion Preparation Example 1

20 parts by weight of a PB-821 containing a mixture of CI Pigment Red 254 and CI Pigment Red 177 by weight of 80/20 and 6 parts by weight (based on solids) as a dispersing agent as a coloring agent (A) using a bead mill A pigment dispersion (R) was prepared by using 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 2

20 parts by weight of a mixture comprising CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 138 by weight ratio of 50/30/20, 5 parts by weight (based on solids) as a colorant (A) using a bead mill A pigment dispersion (G) was prepared as BYK-2001 as a dispersing agent and 75 parts by weight of a propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 3

20 parts by weight of a carbon black as a colorant (A), 3 parts by weight (as solid) of BYK-2001 as a dispersing agent, and 75 parts by weight of a propylene glycol monomethyl ether acetate as a solvent were treated using a bead mill Ester, a pigment dispersion (BK) was prepared.

Example 1

By mixing 100 parts by weight of the pigment dispersion (R) as a colorant (A), 15 parts by weight (based on solids) as an alkali-soluble resin ( B) Alkali-soluble resin (B-1), 15 parts by weight as difunctional pentaerythritol hexaacrylate of polyfunctional monomer (C), 5 parts by weight as photoinitiator (D) 2 -Methyl-1-[4-(methylthio)phenyl]-2-morpholinanpropan-1-one and propylene glycol monomethyl ether acetate as a solvent, so that the solid concentration becomes 20% by weight, and A liquid composition (R1) was prepared.

A pattern was formed using the liquid composition (R1) and evaluated in the following manner. The results of the assessment are shown in Table 6.

Pattern formation

The liquid composition (R1) was applied to the surface of 6 glass substrates using a spin coater, followed by prebaking at 90 ° C for 4 minutes to form a coating film having a film thickness of 1.3 μm. Thereafter, the substrate was cooled to room temperature, and the coating film on each substrate was exposed to a high pressure mercury lamp through a photomask at an exposure of 100, 200, 300, 400, 500, 750 or 1,000 Joules/m ² . Thereafter, the coating film on each substrate was sprayed with a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C at a development pressure of 1 kg/mm ² (nozzle dispersant: 1 mm) for spray development, followed by 220 ° C. After baking for 30 minutes to form a dot pattern of 200 μm × 200 μm.

Sensitivity assessment

The dot pattern formed by each exposure amount on each substrate was observed by a scanning electron microscope, and the film formation ratio was good when the formed pattern was good and the film thickness ratio before and after development (film thickness after development × 100 / before development) When the film thickness is 90% or more, it is evaluated as "○", and the formed pattern is good, but the film retention percentage is less than 90% or the pattern portion is broken, and it is evaluated as "△". It is rated as "X" when no pattern is formed.

Evaluation of solvent resistance

Three substrates with an exposure exposure of 1,000 J/m ^{2 were} immersed in 25 ° CN-methylpyrrolidone (indicated by "NMP" in Tables 6 to 9) and a 5 wt% aqueous sodium hydroxide solution (Tables 6 to 9). "NaOH" or 18% by weight of hydrochloric acid (indicated by "HCl" in Tables 6 to 9). The dot pattern before and after the immersion was observed by a scanning electron microscope over a period of 30 minutes, and the formed pattern was good and the film was immersed before and after immersion. When the thickness ratio (film thickness after immersion × 100 / film thickness before immersion) was 95% or more, it was evaluated as "○", and when the film thickness ratio before and after immersion was less than 95% or the pattern portion was broken, it was evaluated as "△". When the entire pattern was detached from the substrate after immersion, it was rated as "X".

Adhesion assessment

The liquid composition (R1) was applied to the surface of the glass substrate by a spin coater, and baked at 90 ° C for 4 minutes to form a 1.3 μm thick coating film. After the substrate was cooled to room temperature, the coating film was exposed to a 2,000 Joule/m ² exposure with a high pressure mercury lamp. Thereafter, the coating pressure was sprayed on a developing pressure of 1 kg/mm ² (nozzle dispersant: 1 mm) with a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C for spray development, followed by post-baking at 220 ° C. minute. Thereafter, the coating film was cut into 100 squares in accordance with the JIS K5400 standard to evaluate the adhesion. ○ indicates no square peeling, △ indicates that there are 1 to 10 squares peeling off, and × indicates that there are more than 10 squares peeling off.

Examples 2 to 41 and Comparative Examples 1 to 20

The liquid composition was prepared and evaluated in the same manner as in Example 1. The types and amounts of the different parts were changed as shown in Tables 2 to 5 (wherein "parts" means "parts by weight"). The results of the evaluation are shown in Tables 6 to 9.

In Tables 2 to 5, the polyfunctional monomer and the photopolymerization initiator are shown by the following symbols.

Polyfunctional monomer

C-1: diisopentyltetraol hexaacrylate C-2: trimethylolpropane triacrylate

Photopolymerization initiator

D-1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinpropan-1-one D-2: 2-benzyl-2-dimethylamino- 1-(4-morpholinylphenyl)butan-1-one D-3: 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]- Ethyl ketone 1-(O-acetamidine) D-4: 4,4'-bis(diethylamino)diphenyl ketone D-5: 2,4-diethylthiaxanone D- 6:2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbylphenyl)-1,2'-biimidazole D-7: 2-mercaptobenzothiazole

As described above, the radiation-sensitive composition for forming a color layer of the present invention does not reduce the film retention percentage and cause pattern breakage and side etching even at a low exposure amount, and can form a solvent resistance and adhesion to a substrate. And other pixels and black matrix with excellent properties, and even when containing a high concentration of pigment, exhibit excellent storage stability in the form of a liquid composition, and constitute a main component of the alkali-soluble resin (B) (ie, a binder component) The copolymer (B1) has good storage stability.

Accordingly, the radiation-sensitive composition of the present invention for forming a color layer is highly suitable for use in the manufacture of various color filters, including color filters for color liquid crystal display elements in the electronics industry.

Claims (10)

A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, and is used to form a colored layer, the base The soluble resin (B) comprises a reproducing unit represented by the following formula (1) having at least one group selected from the group consisting of an acid functional group and an acid anhydride group: (wherein R ⁷ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms), and a group represented by the following formula (2): (wherein X represents an n-valent organic group, R ⁸ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, n represents an integer of 2 to 10, and "*" represents a bonding hand) The polymer. The radiation-sensitive composition according to claim 1, wherein the group represented by the former formula (2) in the alkali-soluble resin (B) is a group represented by the following formula (3): (wherein Y represents an n-valent organic group, R ⁸ and n are as defined in formula (2), and "*" is a bond). The radiation-sensitive composition of claim 1, wherein the alkali-soluble resin (B) comprises a copolymer obtained by polymerizing a mixture, the polymerizable mixture comprising (b1) selected from the group consisting of unsaturated carboxylic acids, and unsaturated a group of at least one compound composed of a carboxylic anhydride and an unsaturated phenol compound and (b2) a compound represented by the following formula (4): (wherein R ⁷ is as defined in formula (1)) and its polymerization is carried out in the presence of a compound represented by the following formula (5): (where X, R ⁸ and n are as defined by formula (2)). The radiation-sensitive composition of claim 3, wherein the polymerizable mixture further comprises (b3) an unsaturated compound having an oxetane structure and/or an unsaturated compound having a tetrahydrofuran structure. The radiation-sensitive composition of claim 1, wherein R ⁷ in the formula (1) is a cyclohexyl group or a phenyl group. A radiation-sensitive composition according to claim 3, wherein the compound represented by the formula (4) is N-cyclohexylmethyleneimine or N-phenylmethyleneimine. A color filter comprising a color layer formed using the radiation-sensitive composition of any one of claims 1 to 6. A color liquid crystal display element comprising the color filter of item 7 of the patent application. A method for producing an alkali-soluble resin, comprising a polymerizable polymerizable mixture, the polymerizable mixture comprising (b1) at least one compound selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic anhydrides, and unsaturated phenolic compounds and B2) A compound represented by the above formula (4), which is polymerized in the presence of a compound represented by the above formula (5). The method of claim 9, wherein the compound of the formula (4) is N-cyclohexylmethyleneimine or N-phenylmethyleneimine.