TWI398454B - Polymer, radiation sensitive composition for color filters, color filter and color liquid crystal display device or panel - Google Patents

Description

Polymer, ray-sensitive composition for color filters, color filters, and color liquid crystal display devices or panels

The present invention relates to a radiation sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device or panel. More particularly, it relates to a ray-sensitive composition for forming a colored layer (pixel and/or black matrix) that can be used to fabricate a color liquid crystal display for use in transmitting and reflecting or A color filter of a panel or a color image pickup device, a color filter including a colored layer made of a radiation sensitive composition, and a color liquid crystal display device including the color filter.

As a method of manufacturing a color filter by using a colored ray composition, there is known a method in which a ray ray composition is applied to a substrate or a substrate including a light shielding layer having a desired pattern and dried and then the desired pattern The dried coating film is exposed to radiation (hereinafter referred to as "exposure") and developed to obtain pixels (see JP-A 2-144502 and JP-A 3-53201) (the term "JP-A" is used herein) It refers to an “uncensored open Japanese patent application”).

However, in the technical field of color filters, there is a strong tendency to cut the tact time by reducing the amount of exposure, but shortening the tact time makes it difficult to obtain an excellent pixel pattern and a black matrix pattern because The edge of the pattern obtained by the inventive colored ray composition tends to be partially absent or undercut at the time of development.

Summary of invention

It is an object of the present invention to provide a radiation-sensitive composition for forming a colored layer which exhibits excellent developability, and more particularly, a novel radiation-sensitive composition for a color filter which is not developed during development. The edges of the pattern create undissolved product or scum and provide a missing portion or undercut of the pixel and black matrix without pattern edges, even when the amount of exposure is small, a component that can be used as a composition. A polymer, a color filter formed from a radiation ray composition for a color filter, and a liquid crystal display device including the color filter.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, first, the object and the object of the present invention described above are achieved by a polymer (hereinafter referred to as "polymer (A)") by making (a1) an unsaturated carboxylic acid and/or unsaturated. A copolymer of a carboxylic acid anhydride, a compound containing at least one hydroxyl group in (a2) molecule, and (a3) another unsaturated compound is obtained by reacting with an isocyanate compound represented by the following formula (1): Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a group represented by the following formula (I) or (II), provided that R ₁ , R ₂ and R _{3 are} not simultaneously a hydrogen atom, and a , b, c and d are each independently an integer from 0 to 12.

According to the present invention, secondly, the above objects and advantages of the present invention are achieved by a radiation-sensitive composition for a color filter comprising (A) the above polymer, (B) a colorant, and (C) a polyfunctional Monomer and (D) photopolymerization initiator.

The term "colored layer" as used herein refers to a layer consisting of pixels and/or black matrices used in color filters.

According to the present invention, third, the above objects and advantages of the present invention are achieved by a color filter comprising a colored layer produced by the above-described radiation ray composition for a color filter.

According to the present invention, in the fourth aspect, the above objects and advantages of the present invention are achieved by a color liquid crystal display device or panel including the color filter.

Detailed description of the preferred system

The invention will be disclosed in detail later.

(A) polymer

The polymer (A) in the present invention is obtained by using (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (a2) an unsaturated compound containing at least one hydroxyl group in the molecule, and (a3) another unsaturated compound. The resulting copolymer (hereinafter referred to as "alkali-soluble resin [α]") is obtained by reacting with an isocyanate compound represented by the above formula (1) (hereinafter referred to as "unsaturated isocyanate compound (1)").

The unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (a1) (hereinafter generally referred to as "(a1) unsaturated carboxylic acid compound") among the components of the alkali-soluble resin [α] is, for example, a carboxyl group-containing unsaturated single body. Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids and anhydrides thereof such as maleic acid and maleic acid Anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; unsaturated polycarboxylic acids having three or more carboxyl groups and anhydrides thereof; having two or More mono-((meth)propenyloxyalkyl]esters of polycarboxylates such as mono[2-(methyl)propenyloxyethyl]succinate and mono[2-(methyl) A propylene methoxyethyl phthalate; and a mono (meth) acrylate such as ω-carboxypolycaprolactone mono (meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both ends.

Among these carboxyl group-containing unsaturated monomers, mono(2-propenyloxyethyl) succinate and mono(2-propenyloxyethyl) decanoate are commercially available respectively (Toagosei Chemical Industry Co., Ltd. The company's trade names are M-5 300 and M-54 00.

In the alkali-soluble resin [α], the above unsaturated carboxylic acid compound (a1) may be used singly or in combination of two or more.

In the alkali-soluble resin [α], the content of the repeating unit derived from the unsaturated carboxylic acid compound (a1) is preferably from 5 to 50% by weight, more preferably from 5 to 40% by weight, particularly preferably from 5 to 30% by weight. When the content of the repeating unit derived from the unsaturated carboxylic acid compound (a1) is less than 5 wt%, the solubility of the polymer obtained by reacting with the unsaturated isocyanate compound (1) in an alkaline developer can be lowered and When the content is more than 50% by weight, the solubility of the polymer in the alkaline developer may become too high.

Examples of the unsaturated compound (a2) containing at least one hydroxyl group in the molecule include hydroxyalkyl acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3 -hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,2-dihydroxyethyl acrylate, acrylic acid 2 ,3-dihydroxypropyl ester, 1,3-dihydroxypropyl acrylate, 3,4-dihydroxybutyl acrylate and 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropenyl acrylate Oxy]-2-hydroxypropyl ester; and hydroxyalkyl methacrylates such as 1,2-dihydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, methacryl 1,3 -dihydroxypropyl ester, 3,4-dihydroxybutyl methacrylate and 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropane methacrylate ester.

Among these unsaturated compounds (a2) containing at least one hydroxyl group, 2-hydroxyethyl (meth)acrylate and 1,2-dihydroxyethyl acrylate are from the viewpoints of copolymerization reactivity and reactivity with an isocyanate compound. Esters, 2,3-dihydroxypropyl acrylate, 1,2-dihydroxyethyl methacrylate and 2,3-dihydroxypropyl methacrylate are preferred.

In the alkali-soluble resin [α], the unsaturated compound (a2) containing at least one hydroxyl group in the molecule may be used singly or in combination of two or more.

In the alkali-soluble resin [α], the content of the repeating unit derived from the unsaturated compound (a2) containing at least one hydroxyl group in the molecule is preferably from 1 to 50% by weight, more preferably from 3 to 40% by weight, particularly preferably from 5 to 30 wt%. When the content of the repeating unit derived from the unsaturated compound (a2) containing at least one hydroxyl group in the molecule is less than 1% by weight, the sensitivity may be lowered and the content may be lowered due to a decrease in the ratio of the introduction of the unsaturated isocyanate compound (1) into the polymer. Above 50 wt%, the storage stability of the polymer obtained from the reaction with the unsaturated isocyanate compound (1) may be lowered.

Examples of the other unsaturated compound (a3) 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-vinyl Benzyl methyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether and p-vinyl benzyl epoxy propyl ether; hydrazines such as hydrazine And 1-methylhydrazine; unsaturated carboxylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, methyl n-propyl (meth)acrylate, i-propyl (meth)acrylate, N-butyl (meth)acrylate, i-butyl (meth)acrylate, second-butyl (meth)acrylate, t-butyl (meth)acrylate, allyl (meth)acrylate, Methyl methacrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate Ester, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, methoxy dipropylene glycol (methyl) Acrylate, isodecyl (meth)acrylate, dicyclopentadienyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate; alkoxyalkyl esters of unsaturated carboxylic acids, for example 2-Aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylaminopropyl (meth)acrylate Ester, 3-aminopropyl (meth)acrylate and 3-dimethylaminopropyl (meth)acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl (meth)acrylate; vinyl Cyanating compounds such as (meth)acrylonitrile, α-chloroacrylonitrile and vinyl cyanide; unsaturated amides such as (meth) acrylamide, α-chloropropenylamine and N-2-hydroxyethyl (A) Acrylamide; unsaturated quinone imines such as maleimide, N-phenyl maleimide and N-cyclohexyl maleimide; vinyl carboxylate Such as vinyl acetate, propionic acid Ester esters, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl epoxy propyl ether; aliphatic conjugated dienes such as 1,3 - butadiene, isoprene and chloroform; and macromonomers having a mono(meth)acrylonitrile group at the terminal of the polymer molecular chain such as polystyrene, poly(methyl) methacrylate, poly- N-butyl (meth)acrylate and polyoxyalkylene oxide.

Among these other unsaturated compounds (a3), styrene, methyl (meth)acrylate, (meth)acrylic acid, from the viewpoints of copolymerization reactivity and solubility of the obtained polymer (A) in an aqueous alkaline solution N-propyl ester, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, benzyl (meth)acrylate and N-phenyl-butenylene Yttrium imine is preferred.

In the alkali-soluble resin [α], the other unsaturated compound (a3) may be used singly or in combination of two or more.

In the alkali-soluble resin [α], the content of the repeating unit derived from the other unsaturated compound (a3) is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight, particularly preferably from 30 to 50% by weight. When the content of the repeating unit derived from the other unsaturated compound (a3) is less than 10% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (1) may be lowered and when the content is higher than 70 wt% The solubility of the polymer in the alkaline developer may be lowered.

The alkali-soluble resin [α] can polymerize the unsaturated carboxylic acid compound (a1), the hydroxyl group-containing unsaturated compound (a2), and other unsaturated compounds, for example, by the presence of a radical polymerization initiator in a suitable solvent. Made with a3).

Examples of the solvent used for the above polymerization include alcohols such as methanol, ethanol, n-propanol and i-propanol; ethers such as tetrahydrofuran and dioxane; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether; ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ether propionate such as Ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate and ethylene glycol mono-n-butyl ether propionate; Glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether; dipropylene glycol alkyl ethers such as dipropylene glycol-a Ethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether; propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, Propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate and propylene glycol mono-n-butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-pentyl Ketones, 3-pentanone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; alkyl alkoxypropionates such as methyl 2-methoxypropionate, 2-methoxypropane Ethyl acetate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy N-propyl propyl propionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propoxy propionate Ester, 2-n-propyl N-butyl propyl propionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, 2-n-butoxypropionic acid Butyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, 3-ethoxyl Methyl propionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, 3- Ethyl n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n-butoxy Ethyl propionate, n-propyl 3-n-butoxypropionate and n-butyl 3-n-butoxypropionate; and other esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate Ester, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl glycolate, n-butyl glycolate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, 2-methoxybutyl acetate , 3-ethoxybutyl acetate, 3-propoxybutyl acetate, methyl lactate, ethyl lactate, milk N-propyl ester, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate , n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid N-propyl ester, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, n-propoxyacetate Ester, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetic acid Propyl ester and n-butyl n-butoxyacetate.

Among these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkoxypropionic acid alkyl esters, and acetates are preferred.

The above solvents may be used singly or in combination of two or more.

The above radical polymerization initiator is not particularly limited.

Examples of the radical polymerization initiator include an azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2' - azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-even Nitrogen bis(2-methylpropionate) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzammonium peroxide, Peroxidic lauryl sulfonate, tertiary butyl peroxy isobutyrate and 1,1-bis(t-butylperoxy)cyclohexane; and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, it can be used in combination with a reducing agent as a redox initiator.

These radical polymerization initiators may be used singly or in combination of two or more.

In the present invention, the weight average molecular weight (hereinafter referred to as "Mw") expressed by polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is used for the alkali-soluble resin [α]. Good is 3,000 to 300,000, preferably 5,000 to 100,000.

The amount of the alkali-soluble resin [α] used in the present invention is preferably expressed by polystyrene as measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) (referred to as "Mn"). It is 3,000 to 60,000, more preferably 5,000 to 25,000.

When the Mw is less than 3,000, the alkali developability and film residual ratio of the resulting film may be deteriorated, or the pattern shape and heat resistance may be impaired. When Mw is higher than 300,000, the resolution may be lowered, or the shape of the pattern may be damaged.

In the present invention, the polymer (A) is obtained by reacting an alkali-soluble resin [α] with an unsaturated isocyanate compound (1).

The alkali-soluble resin [α] thus obtained can be used as a polymer solution to produce the polymer (A) directly or after being separated from the solution.

The unsaturated isocyanate compound (1) is represented by the following formula (1):

Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a group represented by the following formula (I) or II), provided that R ₁ , R ₂ and R _{3 are} not simultaneously a hydrogen atom, and a, b, c and d are each independently an integer from 0 to 12.

Examples of the unsaturated isocyanate compound (1) include propylene isocyanates such as 1,1-(bispropenyloxymethyl)ethyl isocyanate, 1,1-(bisacryloxyl byanide) Ethyl ester and 1,1-(bisacryloxypropyl)ethyl isocyanate; and methacrylic isocyanate such as 1,1-(bismethylpropenyloxy) isocyanate Ethyl ester, 1,1-(bismethylpropenyloxyethyl)ethyl isocyanate and 1,1-(bismethylpropenyloxypropyl)ethyl isocyanate.

Among these unsaturated isocyanate compounds (1), 1,1-(bispropenyloxymethyl)ethyl isocyanate and isocyanic acid 1,1 from the viewpoint of reactivity with an alkali-soluble resin [α] - (Dimethacryloxymethyl) ethyl ester is preferred.

Commercial products of the above 1,1-(bisacryloxymethyl)ethyl isocyanate include Karenz BEI (trade name of Showa Denko K.K.).

In the reaction with the alkali-soluble resin [α], the unsaturated isocyanate compound (1) may be used singly or in combination of two or more.

In the present invention, the reaction between the alkali-soluble resin [α] and the unsaturated isocyanate compound (1) can be carried out by dropping the unsaturated isocyanate compound (1) dropwise to the contained contact at room temperature or under nitrogen at an increased temperature. The medium is, for example, a solution of tin (IV) di-n-butyl dilaurate and a polymerization inhibitor such as an alkali-soluble resin [α] of p-methoxyphenol.

The amount of the unsaturated isocyanate compound (1) used for the production of the polymer (A) is preferably from 0.1 to 90% by weight, more preferably from 10 to 80% by weight, particularly preferably from 25 to 75% by weight, which is used for the synthesis of a base. The amount of the hydroxyl group-containing unsaturated compound (a2) of the soluble resin [α] is based on the amount. When the amount of the unsaturated isocyanate compound (1) is less than 0.1% by weight, the effect of improving sensitivity and elasticity is small, and when the amount is more than 90% by weight, the unreacted unsaturated isocyanate compound (1) and the resulting polymerization remain. The storage stability of the solution or the radiation sensitive resin composition may be lowered.

The polymer (A) contains a carboxyl group and/or a carboxylic acid anhydride group and a polymerizable unsaturated bond, has a suitable solubility in an alkali developer, and can be easily hardened by heat without using a hardener. The radiation-sensitive resin composition comprising the polymer (A) does not produce undissolved product or scum at the edge of the pattern at the time of development, and the provided pixel and the black matrix have no missing portions or undercuts of the pattern edges. Even when the amount of exposure is small.

Preferably, the polymer (A) has a structure represented by the following formula (2):

Wherein R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The polymer (A) having the structure represented by the above formula (2) can be used by synthesizing N-phenyl maleimide or N-cyclohexylbutylene in the synthesis of the alkali-soluble resin [α]. The imine is obtained in at least a portion of the other unsaturated compound (a3).

(B) colorant

The colorant in the present invention is not limited to a specific color and is appropriately selected depending on the application purpose of the resulting color filter. It can be a pigment, a dye or a natural coloring matter.

Since the color filter requires high-definition color development and heat resistance, a coloring agent having high color developability and high heat resistance, particularly a coloring agent having high heat decomposition, is used as the coloring in the present invention. The agent is preferred. Therefore, it is preferred to use an organic pigment and an inorganic pigment, and a particularly preferred one is to use an organic pigment or carbon black.

Examples of the above organic pigments are compounds classified into a pigment group according to a color index (CI; issued by The Society of Dyers and Colourists), particularly a compound having the following color index (CI) number: CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 1 39, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 180 and CI Pigment Yellow 185; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, 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 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI pigment orange 71 and CI pigment orange 73; 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 red 1. CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 50:1, CI Pigment Red 52:1, CI Pigment Red 53:1, CI Pigment Red 57, CI Pigment Red 57:1, CI Pigment Red 57:2, CI Pigment Red 58 : 2, CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81:1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90:1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 15 0, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, 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 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, and CI Pigment Red 265; CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4 CI Pigment Blue 15:6 and CI Pigment Blue 60; CI Pigment Green 7 and CI Pigment Green 36; CI Pigment Brown 23 and CI Pigment Brown 25; and CI Pigment Black 1 and CI Pigment Black 7.

These organic pigments can be purified by sulfuric acid recrystallization, solvent cleaning or a combination thereof prior to use.

Examples of the above inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, xanthan, zinc yellow, iron oxide red (iron oxide red (III)), cadmium red, red, Prussian blue, chromium oxide. Green, cobalt green, amber, titanium black, synthetic iron black and carbon black.

In the present invention, the above organic pigment and non-pigment may be used singly or in combination of two or more, or both may be used in combination. E.g. It is preferred to use one or more organic pigments to form pixels, and preferably two or more organic pigments and/or carbon black to form a black matrix.

In the present invention, the surface of each particle of the pigment may be arbitrarily modified with a polymer prior to use. Examples of the polymer used to modify the surface of each particle of the pigment include the polymer disclosed in JP-A 8-259876 and the commercial polymer and oligomer for dispersing the pigment.

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

The dispersing agent is, for example, a cationic, anionic, nonionic, amphoteric, polydecyloxy or fluorine based surfactant.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylphenyl ethers such as polyoxyethylene are positive Octyl phenyl ether and polyoxyethylene n-decyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; Fatty acid modified polyesters; tertiary amine modified polyurethanes; and polyethyleneimines. These surfactants are available on the market (Kinshin Chemical Industry Co., Ltd.) KP, (Kyoeisha Chemical Co., Ltd.) Polyflow, (Tokem Products Co., Ltd.) F Top, (Daily Ink Chemical Industry Co., Ltd.) Megafac, (Focus of Sumitomo 3M Co., Ltd.), Asahi Guard and Surflon (of Asahi Glass Co., Ltd.), Disperbyk (BYK-Chemical Japan KK), and Solsperse (of Seneka Co., Ltd.) were acquired.

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

The amount of the surfactant is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the coloring agent.

(C) polyfunctional monomer

In the present invention, the polyfunctional monomer is a monomer having two or more polymerizable unsaturated bonds.

Examples of the polyfunctional monomer include alkanediol such as di(meth)acrylate of ethylene glycol and propylene glycol; polyalkylene glycol such as di(meth)acrylate of polyethylene glycol and polypropylene glycol; having 3 or more Hydroxy polyols such as poly(meth)acrylates of glycerol, trimethylolpropane, pentaerythritol and dipentaerythritol and products of their dicarboxylic acid modification; oligo(meth)acrylates such as polyester, Epoxy resin, urethane resin, acid alcohol resin, oxime resin and spiro resin; polymer having hydroxyl group at both ends, for example, poly-1,3-butadiene having hydroxyl group at both ends, at the two ends a poly(isoprene) of a hydroxyl group and a di(meth)acrylate of a polycaprolactone having a hydroxyl group at both ends; and a [2-(methyl)propenyloxyethyl]phosphate.

Among these polyfunctional monomers, a poly(meth) acrylate having a polyhydric alcohol having 3 or more hydroxy groups and a dicarboxylic acid-modified product thereof are preferred, and trimethylolpropane triacrylate, trishydroxyl Propane trimethacrylate, neopentyl alcohol triacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol Examples of the acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the compounds represented by the following formulas (3) and (4) are exemplified.

Among these, trimethylolpropane triacrylate, neopentyl alcohol triacrylate, and dipentaerythritol hexaacrylate are particularly preferred because they provide a colored layer having high strength and excellent surface smoothness on the substrate and No stain or film residue is formed on the unexposed portion of the light-shielding layer.

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

The amount of the polyfunctional 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 polymer (A). When the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer may be deteriorated and when the amount is more than 500 parts by weight, the alkali developability may be lowered, or in the substrate and the unexposed portion. Smudges or film residues may form on the shading layer.

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

Examples of the above monofunctional monomer include a compound such as the above-mentioned carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer, N-(meth)acryl fluorenyl porphyrin, which is listed in the above polymer (A), N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and commercial product M-5600 (trade name, manufactured by Chemical Industry Co., Ltd.).

These monofunctional monomers may be used singly or in combination of two or more. The amount of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. When the amount of the monofunctional monomer is more than 90% by weight, the strength and surface smoothness of the resulting colored layer may become unsatisfactory.

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 [α]. When the total amount is less than 5 parts by weight, the strength and surface smoothness of the colored layer may be deteriorated and when the total amount is more than 500 parts by weight, the alkali developability may be lowered, or on the light shielding layer of the substrate and the unexposed portion. It may produce stains or film residues.

(D) Photopolymerization initiator

The photopolymerization initiator can be formed in the present invention to form the above polyfunctional monomer upon exposure to radiation (referred to as "exposure"), such as visible radiation, ultraviolet radiation, far ultraviolet radiation, electron radiation or X-radiation. (C) A compound of the active species which is polymerized with a selective monofunctional monomer.

(E) Examples of the photopolymerization initiator include a biimidazole compound, a benzoin compound, an acetophenone compound, a diphenylketone compound, an α-diketone compound, a polynuclear quinine compound, Ketone (xanthone) compound, phosphine compound and three Compound.

In the present invention, the above photopolymerization initiators may be used singly or in combination of two or more. In the present invention, the photopolymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound, a biimidazole compound, and three A group consisting of a compound and an O-mercaptopurine compound.

Examples of the above biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4' ,5,5'-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'-biimidazole, 2,2'- Bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4,6-tribromobenzene Base 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-1,2'-biimidazole is particularly preferred.

The biimidazole compound described above has excellent solubility in a solvent, does not produce the aforementioned substances such as insoluble products and precipitates, has high sensitivity, and the hardening reaction is completely promoted by exposure using a small amount of energy source, providing high contrast and unexposed Some do not cause a hardening reaction. Therefore, the coating film obtained after the exposure is clearly divided into a hardened portion in which the developer is insoluble and an uncured portion having high solubility in the developer, whereby it is possible to form a predetermined pixel pattern and a predetermined black matrix. A high resolution image array with no undercuts.

-hydrogen donor-

When a biimidazole compound is used as the photopolymerization initiator of the present invention, it is preferably used in combination with the following hydrogen donor to further improve the sensitivity.

The term "hydrogen donor" as used herein denotes a compound which provides a hydrogen atom by exposure to form a free radical from a biimidazole compound.

The hydrogen donor is preferably a thiol compound defined below or an amine compound defined below.

The above thiol compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and one or more, preferably 1 to 3, more preferably 1 or 2 fluorenyl groups bonded directly to the mother nucleus (hereinafter referred to as " Thiol hydrogen donor").

The above amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and one or more, preferably 1 to 3, more preferably 1 or 2, amine groups directly bonded to the mother nucleus (hereinafter referred to as " Amine hydrogen donor").

These hydrogen donors may have both a mercapto group and an amine group.

A detailed description of the hydrogen donor is then given.

The thiol hydrogen donor can have at least one benzene or heterocycle, or both. A fused ring may or may not be formed when it has two or more rings.

When the thiol hydrogen donor has two or more thiol groups, at least one other thiol group may be substituted with an alkyl group, an aralkyl group or an aryl group, with respect to at least one free thiol group. Further, in terms of at least one free thiol group, the thiol hydrogen donor may have a structural unit in which two sulfur atoms are bonded together by a divalent organic group such as an alkyl group, or two of the sulfur atoms are bonded together A structural unit in the form of a disulfide.

Further, the thiol hydrogen donor may be substituted at the non-fluorenyl group with a carboxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group or a nitrile group.

Examples of the 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.

The amine hydrogen donor can have at least one benzene or heterocycle, or both. When it has two or more rings, a fused ring may or may not be formed.

At least one amine group of the amine hydrogen donor may be substituted with an alkyl group or a substituted alkyl group. The amine hydrogen donor may be substituted at the non-amino group by a carboxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group or a nitrile.

Examples of the above amine hydrogen donor include 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4-diethylaminophenyl benzene. Ketone, 4-dimethylaminopropenylbenzene, ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid and 4-dimethylamine Benzobenzonitrile.

Among these amine hydrogen donors, 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone are preferred, and 4,4'- Bis(diethylamino)diphenyl ketone is particularly preferred. 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone are themselves useful as photo-induced free radical initiators, even when the biimidazole compound is not When it exists.

In the present invention, the above hydrogen donors may be used singly or in combination of two or more. It is preferred to use a composition of at least one thiol hydrogen donor and at least one amine hydrogen donor because the formed colored layer hardly falls from the substrate during development and has high strength and sensitivity.

Examples of preferred compositions of the thiol hydrogen donor and the amine hydrogen donor include a composition of 2-mercaptobenzothiazole/4,4'-bis(dimethylamino)diphenyl ketone, 2-mercaptobenzoene. a composition of thiazole/4,4-bis(diethylamino)diphenyl ketone, a composition of 2-mercaptobenzoxazole/4,4'-bis(dimethylamino)diphenyl ketone, and A composition of 2-mercaptobenzoxazole/4,4'-bis(diethylamino)diphenyl ketone. Composition of 2-mercaptobenzothiazole/4,4'-bis(diethylamino)diphenyl ketone and 2-mercaptobenzoxazole/4,4'-bis(diethylamino)diphenyl The composition of the ketone is more preferred, and the composition of 2-mercaptobenzothiazole/4,4'-bis(diethylamino)diphenyl ketone is particularly preferred.

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

Examples of the above benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2-benzylidenebenzoic acid. Methyl ester.

Examples of the above acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2 -hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl)-2-morpholine-1-propan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1 , 2-diphenylethan-1-one.

Examples of the above diphenyl ketone compound include 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone.

Examples of the above α-diketone compound include diethyl fluorenyl, dibenzoguanidinyl and methyl benzhydrylcarboxylate.

Examples of the above polynuclear quinine compound include hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1,4-naphthol quinone.

Above Examples of ketone (xanthone) compounds include Ketone, oxysulfide Star (thioxanthone) and 2-chlorosulfur star.

Examples of the above phosphine compound include bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Above three Examples of the compound include a compound having a halomethyl group such as 2,4,6-para(trichloromethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three And compounds represented by the following formulas (5) and (6).

The above O-indenyl hydrazine compound is, for example, a compound represented by the following formula (7) or (8).

In the above formulae (7) and (8), R ₁ is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R ₂ and R ₃ each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (having at least one having 1 to 6 carbon atoms) An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom substituted) or an alicyclic group having 7 to 20 carbon atoms (excluding the above cycloalkyl group), and R ₄ is one selected from a hydrogen atom, an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, and a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, R ₅ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, n is an integer of 1 to 5, m is an integer of 0 to 5, and 1 is an integer of 0 to 6. The prerequisite is n+m≦5.

In the above formulae (7) and (8), examples of the linear or branched alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms represented by R ₁ include a methyl group, Ethyl, n-propyl, i-propyl, n-butyl, di-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, N-decyl, n-dodecyl, cyclopentyl and cyclohexyl.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms represented by R ₂ and R ₃ include methyl group, ethyl group, n-propyl group, i- Propyl, n-butyl, second-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-decyl, n-dodeyl , cyclopentyl and cyclohexyl.

The alkyl group having 1 to 6 carbon atoms as a substituent of the phenyl group represented by R ₂ and R ₃ may be linear, branched or cyclic, and may be methyl, ethyl, n-propyl or i-propyl. Examples of the group, n-butyl group, second-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group and cyclohexyl group.

The alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and may be methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy and t-butyl. An example of an oxy group. Examples of the halogen atom include a fluorine atom and a chlorine atom.

Examples of the alicyclic group having 7 to 20 carbon atoms (excluding the above cycloalkyl group) include a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a tertiary-cycloalkyl group, a base containing a terpene skeleton, and A group containing an adamantyl skeleton.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms represented by R ₄ , the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms include a thiophene group. Thioranyl, aziridine, dihydroindolyl, dioxoranyl, three Base, oxygen and sulfur Oxthianyl, thiazolyl, two Oxadizinyl, two Dioxaindanyl, dihyanaphthalenyl, furyl, thiophenyl, pyrrole, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazolyl, piperazine Meryl, pyridyl, anthracene Base, pyrimidinyl, pyridyl Base, pyrroline group, morphonyl, piperazine base, Pyridyl, fluorenyl, isodecyl, benzofuranyl, benzothiophenyl, hydrazine base, Alkenyl, quinolyl, isoquinolyl, indenyl, quinazolinyl, porphyrinyl, anthracene Base, acridinyl, carbazolyl, acridinyl, phenanthryl, thioxanthenyl, brown Thiophene Glycosylthiophene Base, thianthrenyl, tetrahydrofuran and tetrahydropyranyl. Among these, tetrahydrofuran and tetrahydropyranyl are preferred.

The alkyl group having 1 to 12 carbon atoms represented by R ₅ may be linear, branched or cyclic, and may be methyl, ethyl, n-propyl, i-propyl, n-butyl or second-butyl. For example, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-decyl, n-dodecyl, cyclopentyl and cyclohexyl groups.

The alkoxy group having 1 to 12 carbon atoms may be linear, branched or cyclic, and may be methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy or t-butyl. The oxy group and the n-pentyloxy group are exemplified.

Among these, methyl, ethyl, n-propyl, i-propyl, n-butyl, methoxy and ethoxy groups are particularly preferred.

n is preferably 1. m is preferably 0, 1 or 2, and particularly preferably 1.1 is preferably 0, 1 or 2, particularly preferably 1.

Illustrative examples of O-mercaptopurine compounds include 1-[9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-decane-1,2-decane-2-肟-O-benzoate, 1-[9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-nonane-1,2-decane-2-indole -O-acetate, 1-[9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-pentane-1,2-pentane-2-indole-O -acetate, 1-[9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-oct-1-one oxime-O-acetate, 1-[9 -ethyl-6-(2-methylbenzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9- Ethyl-6-(2-methylbenzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-acetate, ethyl ketone, 1-[9 -ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl), Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzylidene)-9.H.-carbazol-3-yl -, 1-(O-ethylhydrazinyl), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzylidene)-9.H.- Oxazol-3-yl]-, 1-(O-acetamidoxime) and ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl methoxybenzene Mercapto)-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl).

The above photopolymerization initiators may be used singly or in combination of two or more.

The total amount of the photopolymerization initiator in the present invention is preferably from 0.01 to 200 parts by weight, more preferably from 1 to 120 parts by weight, particularly preferably from 1 to 100 parts by weight, based on 100 parts by weight of the polyfunctional monomer (C). The basis is based on the sum of 100 parts by weight of the component (C) and optionally used monofunctional monomers. When the total amount of the photopolymerization initiator is less than 0.01 parts by weight, it may be difficult to obtain an image array having a predetermined pixel pattern and a predetermined black matrix pattern due to incomplete hardening of exposure. When the total amount is more than 200 parts by weight, the formed colored layer may fall from the substrate during development and may cause stains or film residues on the substrate and the unexposed portion of the light shielding layer.

In the present invention, the above photopolymerization initiator may be used in combination with at least one sensitizer, hardening accelerator, and polymer optical crosslinking/sensitizer as needed.

-additive-

The radiation sensitive composition for use in the color filter of the present invention contains the above components (A) to (D) as essential components and optionally other additives.

The above additives include an organic acid or an organic amine based compound (excluding the above hydrogen donor) for further improving the solubility in the alkaline developer of the radiation sensitive composition and further suppressing the generation of insoluble product residues after development.

The above organic acid is preferably an aliphatic carboxylic acid having at least one carboxyl group in the molecule or a phenyl-carboxylic acid-containing compound.

Examples of the above aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, ethantic acid, and octanoic acid; Acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecane dibasic acid, methylmalonic acid, ethyl Malonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and medium And acid: and tricarboxylic acids such as citric acid, aconitic acid and camphoric acid.

The phenyl group-containing carboxylic acid is, for example, a compound having a carboxyl group directly bonded to a phenyl group or a carboxylic acid having a carboxyl group bonded to a phenyl group via a carbon chain.

Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, anisic acid, 2,3-xylenecarboxylic acid, and 3,5-xylenecarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid. , isophthalic acid and terephthalic acid; aromatic polycarboxylic acids having 3 or more carboxyl groups such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3 , 5-benzenetetracarboxylic acid and pyromellitic acid; and phenylacetic acid, hydrogen ato acid, hydrogen cinnamic acid, phenylglycolic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamylidenic acid, Coumaric acid and umbrella acid.

Among these organic acids, from the viewpoint of alkaline solubility, solubility in a solvent which will be described later, and prevention of stains or film residues on the light-shielding layer of the substrate and the unexposed portion, as a fat Grouped carboxylic acids, aliphatic dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid and mesaconic acid are particularly preferred. As the phenyl group-containing carboxylic acid, an aromatic dicarboxylic acid is preferred, and phthalic acid is particularly preferred.

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

The amount of the organic acid is preferably 15 wt% or less, more preferably 10 wt%, which is based on the entire radiation composition. When the amount of the organic acid is more than 15% by weight, the adhesion to the substrate on which the colored layer is formed may be lowered.

The above organic amine-based compound is preferably an aliphatic amine or a phenylamine having at least one amine group in the molecule.

Examples of the above aliphatic amines include mono(cyclo)alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, second-butylamine, t-butylamine, n-pentylamine, n-hexylamine, and Heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclo Hexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine and 4-ethylcyclohexylamine; di(cyclo)alkylamines such as methylethylamine, diethylamine, methyl n-propylamine, B Base n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-second-butylamine, di-t-butylamine, di-n-pentylamine, two - 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-i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-second- Butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexane , diethyl cyclohexylamine, methyl dicyclohexylamine, ethyl dicyclohexylamine and tricyclohexylamine; mono(cyclo)alkanolamines such as 2-aminoethanol, 3-amino-1-propane Alcohol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol and 4-amino-1-cyclohexane Alcohol; di(cyclo)alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine , di-n-hexanolamine and bis(4-cyclohexanol)amine; tri(cyclo)alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine , tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine and tris(4-cyclohexanol)amine; amine (cyclo)alkanediols such as 3-amino-1,2 -propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-ring Hexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino -1,3-propane And 2-diethylamino-1,3-propanediol; amine-containing cycloalkane methanols such as 1-aminocyclopentane methanol, 4-aminocyclopentane methanol, 1-aminocyclohexane methanol, 4-aminocyclohexane methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol, and 4-diethylaminocyclohexane Alkanol; and aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid.

The above phenyl group-containing amine is, for example, a compound having an amine group directly bonded to a phenyl group, or a compound having an amine group bonded to a phenyl group via a carbon chain.

Examples of the phenyl group-containing amine include aromatic amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i- Propylaniline, 4-n-butylaniline, 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline and 4-methyl Benzyl-N,N-dimethylaniline; aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol and 4-di Ethyl benzyl alcohol; and amino phenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol and 4-diethylaminophenol.

Among these organic amine-based compounds, as an aliphatic amine, from the viewpoints of solubility in a solvent to be described later and prevention of stains or film residues on the light-shielding layer of the substrate and the unexposed portion, (Cyclo)alkanolamines and amine (cyclo)alkanediols are preferred, and 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. As the phenyl group-containing amine, an aminophenol is preferred, and 2-aminophenol, 3-aminophenol and 4-aminophenol are particularly preferred.

The above organic amine-based compounds may be used singly or in combination of two or more.

The amount of the organic amine-based compound is preferably 15% by weight or less, more preferably 10% by weight or less, based on the entire radiation absorbing composition. When the amount of the organic amine-based compound is more than 15% by weight, the adhesion to the substrate on which the colored layer is formed may be lowered.

In addition to the above organic acid and organic amine based compound, the additive includes a dispersing aid such as a blue pigment derivative or a yellow pigment derivative, for example, a copper indigo derivative; a filler such as glass or alumina; a polymer compound such as polyethylene. Alcohol, polyethylene glycol monoalkyl ether or poly(fluoroalkyl acrylate); nonionic, cationic or anionic surfactant; adhesion accelerators such as vinyl trimethoxy decane, vinyl triethoxy decane, Vinyl ginseng (2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropyl. methyl. Dimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropyl. methyl. Dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl. methyl. Dimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane; antioxidants such as 2,2'-sulfur (4-methyl-6-t-butylphenol) or 2,6-di-t-butylphenol; UV absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxybenzene -5-chlorobenzotriazole or alkoxydiphenyl ketone; cohesion inhibitor such as sodium polyacrylate; and thermal radical generator such as 1,1'-azobis(cyclohexane-1-methyl) Nitrile) or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent

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

A suitable solvent can be selected and used as a solvent insofar as it disperses or dissolves the components (A) to (D) and additives which constitute the radiation-sensitive composition, does not react with these and has appropriate volatility.

Examples of the solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether , triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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 mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acid esters and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as a base Ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactates such as methyl lactate and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, 3-methyl Methyl oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl 3-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, acetic acid Propyl ester, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid I-propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate and ethyl 2-ketobutyrate; aromatic hydrocarbons For example, toluene and xylene; and guanamines and endoxines such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether from the viewpoints of solubility, pigment dispersibility, and coatability Acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate , 3-ethoxypropionate methyl ester, 3-ethoxypropionic acid ethyl ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, formic acid Amyl ester, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate are particularly preferred.

The above solvents may be used singly or in combination of two or more.

Further, a high boiling point solvent such as benzylethyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate Ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate can be used together with the above solvents.

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

The amount of the solvent is not particularly limited, but from the viewpoint of coatability and stability of the resulting radiation-sensitive composition, it is desirable to ensure that the total amount of all components other than the solvent of the composition is usually 5 to 50% by weight, preferably 10 To a value of 40 wt%.

Color filter

The color filter of the present invention comprises a colored layer produced from a radiation sensitive composition forming the colored layer of the present invention.

The method of forming the color filter of the present invention is then given.

Optionally arbitrarily formed on the surface of the substrate to the light-shielding layer to define a portion forming the pixel, and a liquid radiation ray composition comprising, for example, a red pigment dispersed therein, applied to the substrate and pre-baked to evaporate the solvent to form Coating film. The coating film is then exposed to radiation through a reticle, developed with an alkaline developer to dissolve and remove the unexposed portions of the coating film and post-baked to form a red pixel array having a predetermined pixel pattern.

Thereafter, application, prebaking, exposure, development, and post-baking of the liquid radiation ray composition containing the green and blue pigment dispersed therein are similarly performed to subsequently form a green pixel array and a blue pixel array on the same substrate. A color filter having an array of red, green, and blue pixels on the substrate is obtained. The order in which the color pixels are formed is not limited to those described above in the present invention.

Similarly, a black matrix can be formed by using a radiation ray composition for forming the colored layer of the present invention.

The substrate used to form the pixel and/or black matrix is made of glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamido-imine or polyimine.

The substrate may be optionally subjected to a suitable pretreatment such as chemical treatment with a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction or vacuum deposition.

In order to apply the liquid radiation ray composition to the substrate, suitable coating techniques such as spraying, roll coating, spin coating (spin coating), slit die coating, strip coating or inkjet coating may be employed. . Among these, spin coating and slot die coating are preferred.

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.

The radiation used to form the pixels and/or the Black matrix is selected from the group consisting of visible radiation, ultraviolet radiation, far ultraviolet radiation, electron radiation, and X-radiation. Among these, radiation having a wavelength of 190 to 450 nm is preferred.

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

The above alkaline developer is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium chloride, choline or 1,8-diazabicyclo-[5.4.0]-7-undecene. Or an aqueous solution of 1,5-diazabicyclo-[4.3.0]-5-decene.

A suitable amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the above alkaline developer. The coating film is preferably rinsed with water after alkaline development.

The wet development, the spray development, the dipping (immersion) development or the slurry development may be employed. For the development conditions, the coating film is preferably developed at normal temperature for 5 to 300 seconds.

The color filter of the present invention thus obtained is extremely useful for transmitting and reflecting a color liquid crystal display, a color image pickup device, a color sensor, and the like.

Color liquid crystal display device or panel

The color liquid crystal display device or panel of the present invention comprises the color filter of the present invention.

As an example of the color liquid crystal display device or panel of the present invention, a color liquid crystal display device or panel having excellent characteristics can be fabricated using a radiation sensitive composition forming the colored layer of the present invention to form pixels on the thin film transistor substrate array and/or Or Black matrix.

The radiation sensitive composition forming the colored layer of the present invention contains the above components (A) to (D) as essential components. An example of a particularly good composition is given below.

(1) A radiation-sensitive composition for forming a colored layer comprising (A) a polymer having an ethylenically unsaturated double bond in a side chain (2), a radiation-sensitive composition forming a colored layer (1), which comprises at least a group selected from the group consisting of trimethylolpropane triacrylate, neopentyl alcohol triacrylate, and dipentaerythritol hexaacrylate as the polyfunctional monomer (C) (3) colored layer (2) a radiation-sensitive composition comprising at least one selected from the group consisting of 2-methyl-4-(4-methylthiophenyl)-2-morpholine-1-propan-1-one, 4-(2-hydroxyethoxyl) Phenyl-(2-hydroxy-2-propyl)one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 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, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4,'-double (diethyl Amino)diphenyl ketone, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 1-[9-ethyl-6-(2-methylbenzhydryl) -9.H.-carbazole- 3-yl]-ethane-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene) -9.H.-carbazol-3-yl]-, 1-(O-ethylhydrazinium), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydroperiplatin喃-methoxymethoxybenzhydryl)-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-( 2-methyl-5-tetrahydrofuranylmethoxybenzylidene)-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl) and ethyl ketone, 1-[9 -ethyl-6-(2-methyl-5-tetrahydropiperidylmethoxybenzylidene)-9.H.-carbazol-3-yl]-, 1-(O-ethenyl) a group consisting of, as a photopolymerization initiator (D) (4), a ray-forming composition of the colored layer (1), (2) or (3), comprising an organic pigment and/or carbon black as a colorant ( B) The preferred color filter (5) of the present invention comprises a pixel and/or a black matrix made of a radiation-sensitive composition forming the colored layer (1), (2), (3) or (4). .

The preferred color liquid crystal display device or panel (6) of the present invention comprises the above color filter (5) and the preferred color liquid crystal display device (7) of the present invention comprises a colored layer formed on the thin film transistor substrate array (1) , (2), (3), or (4) a pixel and/or a black matrix manufactured by the radiation ray composition.

As described above, when the radiation ray composition for forming the colored layer of the present invention contains a polymer having an ethylenically unsaturated double bond in a side chain, even if it contains a high concentration of pigment, it is not insoluble during development. The product remains on the substrate and the unexposed light-shielding layer, no scum is formed on the edge of the pixel pattern and the black matrix pattern edge, and a small amount of exposure can form an excellent pixel pattern and a missing portion without a pattern edge or Undercut black matrix pattern.

Further, the pixel and black matrix fabricated from the radiation-sensitive composition for forming the colored layer of the present invention have high surface smoothness and excellent adhesion to the substrate.

Therefore, the radiation ray composition for forming the colored layer of the present invention can be extremely advantageously used for the manufacture of color filters such as color liquid crystal display devices or color filters of panels in the electronics industry.

Instance

The following examples are provided to further illustrate the invention but are not to be considered as limiting.

In the following examples, "parts" and "%" are based on weight.

Each Mw and Mn of the resin obtained in the synthesis example was measured by gel permeation chromatography (GPC).

Instrument: GPC-101 column (showa Denko K.K.): GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination. Mobile phase: tetrahydrofuran containing 0.5 wt% phosphoric acid

Synthesis Example 1

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed to a flask equipped with a cooling tube and a stirrer, and then 15 parts by weight of methyl group Acrylic acid, 18.8 parts by weight of N-phenyl maleimide, 35 parts by weight of benzyl methacrylate, 11.2 parts by weight of styrene, 10 parts by weight of 2-hydroxyethyl methacrylate, 10 Parts by weight of ω-carboxy-polycaprolactone monoacrylate and 5 parts by weight of α-methylstyrene dimer as a chain transfer agent and a molecular weight controlling agent are fed to the flask, the inside of the flask is replaced by nitrogen, and The reaction solution was heated at 80 ° C while being gently stirred to polymerize by maintaining the temperature for 3 hours. Thereafter, the reaction solution was further heated at 100 ° C, 0.5 part by weight of 2,2'-azobisisobutyronitrile was added, and polymerization was further continued for another hour to obtain a resin solution (solid content of 33.0 wt%). The obtained resin had a Mw of 12,000 and a (Mw/Mn) ratio of 1.8. This resin was designated as an alkali-soluble resin (α-1).

Thereafter, 10 parts by weight of 1,1-(bispropenyloxymethyl)ethyl isocyanate (trade name of Karenz BEI manufactured by Showa Denko KK) and 0.1 part by weight of 4-methoxyphenol plus The reaction was carried out by stirring to the above alkali-soluble resin (α-1) solution at 40 ° C for 1 hour and at 60 ° C for 2 hours. The reaction between the isocyanate group derived from 2-methylpropenyloxyethyl isocyanate and the hydroxyl group of the alkali-soluble resin (α-1) was confirmed by IR (infrared absorption) spectroscopy. As the reaction proceeds, was observed at about 2,270 cm ^{- 1} near derived from isocyanate 1,1- (bis Bing Xixi yloxymethyl) peak ethyl isocyanate groups of the reduction. A polymer solution having a solids content of 35.0 wt% was obtained. This polymer was designated as polymer-1 (A).

Synthesis Example 2

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed to a flask equipped with a cooling tube and a stirrer, and then 13 parts by weight of methyl group was added. Acrylic acid, 77 parts by weight of benzyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 5 parts by weight of α-methylstyrene dimer feed as chain transfer agent and molecular weight controlling agent To the flask, the inside of the flask was replaced with nitrogen, and the reaction solution was heated at 80 ° C while being gently stirred to be polymerized by maintaining the temperature for 3 hours. Thereafter, the reaction solution was further heated at 100 ° C, 0.5 part by weight of 2,2'-azobisisobutyronitrile was added, and polymerization was further continued for another hour to obtain a resin solution (solid content of 33.0 wt%). The resulting resin had a Mw of 17,000 and a (Mw/Mn) ratio of 2.5. This resin was designated as an alkali-soluble resin (α-2).

Thereafter, 10 parts by weight of 1,1-(bispropenyloxymethyl)ethyl isocyanate (trade name of Karenz BEI manufactured by Showa Denko KK) and 0.1 part by weight of 4-methoxyphenol plus The reaction was carried out by stirring to the above alkali-soluble resin solution (α-2) at 40 ° C for 1 hour and at 60 ° C for 2 hours. The reaction between the isocyanate group derived from 1,1-(bisacryloxymethyl)ethyl isocyanate and the hydroxyl group of the alkali-soluble resin (α-2) was confirmed by IR (infrared absorption) spectroscopy. As the reaction proceeds, was observed at about 2,270 cm ^{- 1} near derived from isocyanate 1,1- (bis Bing Xixi yloxymethyl) peak ethyl isocyanate groups of the reduction. A polymer solution having a solids content of 35.0 wt% was obtained. This polymer was designated as Polymer-2 (A).

Example 1

15 parts by weight of a mixture of CI Pigment Red 254/CI Pigment Red 177 in a weight ratio of 80/20 by a ball mill as a colorant (B), 4 parts by weight (solid content) of Disperbyk-2001 as a dispersing agent, 6 Copolymer of methacrylic acid/N-phenyl maleimide/styrene/benzyl methacrylate (copolymerization weight ratio=20/30/20/30, Mw=9,500, Mn) = 5,000) and 75 parts by weight of propylene glycol monomethyl ether acetate were mixed together as a solvent to prepare an initial dispersion (R1).

Thereafter, 100 parts by weight of the initial dispersion (R1), 7.5 parts by weight of the polymer-1 (A) synthesized in the above Synthesis Example 1 was designated as the polymer (A), and 7.5 parts by weight of dipentaerythritol Alcohol hexaacrylate as polyfunctional monomer (C), 0.5 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 as photopolymerization The agent (D) and 150 parts by weight of ethyl 3-ethoxypropionate and 25 parts by weight of propylene glycol monomethyl ether acetate are mixed together as a solvent to prepare a radiation-sensitive composition (R1) for use in a color filter. -1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the unexposed portion of the substrate and no missing portion and scum were observed on the edge of the pixel pattern.

When the section of the pixel pattern was observed via a scanning electron microscope (SEM), no undercut was seen.

Comparative example 1

(Preparation of liquid composition and formation of colored layer) A radiation sensitive composition (r1-1) was prepared in the same manner as in Example 1, except that the above-mentioned polymer-1 (A) was used instead of the alkali-soluble resin (α-1). other than.

Thereafter, in the same manner as in Example 1, except that the ray ray composition (r1-1) for the color filter was used instead of the ray ray composition (R1-1) for the color filter, A pixel array of green striped pixmaps.

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the unexposed portion of the substrate but a missing portion and scum were observed on the edge of the pixel pattern.

When the section of the pixel pattern is observed via a scanning electron microscope (SEM), the undercut is seen.

Example 2

<Preparation of Liquid Composition and Formation of Colored Layer> A mixture of 15 parts by weight of CI Pigment Green 36/CI Pigment Yellow 138/CI Pigment Yellow 150 in a weight ratio of 50/40/10 was treated in the same manner as in Example 1. As coloring agent (B), 4 parts by weight (solid content) of Disperbyk-2001 as a dispersing agent, 5 parts by weight of methacrylic acid/ω-carboxypolycaprolactone monoacrylate/N-phenylbutylene Copolymer of imine/styrene/benzyl methacrylate/glycerol monomethacrylate (copolymerization weight ratio = 15/10/20/10/35/10, Mw=6,000, Mn=3,000) and 76 A part by weight of propylene glycol monomethyl ether acetate was used as a solvent to prepare an initial dispersion (G1).

Thereafter, 100 parts by weight of the initial dispersion (G1) and 7 parts by weight of the polymer-2 (A) synthesized in the above Synthesis Example 2 were designated as the polymer (A) and 8 parts by weight of the dipentaerythritol. Alcohol hexaacrylate as polyfunctional monomer (C), 0.5 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 as photopolymerization Agent (D), 0.1 part by weight of malonic acid as an additive, and 125 parts by weight of 3-methoxybutyl acetate and 50 parts by weight of propylene glycol methyl ether acetate are mixed together as a solvent to prepare a color filter The ray composition (G1-1) used in the device.

Thereafter, in the same manner as in Example 1, except that the ray ray composition (G1-1) for the color filter was used instead of the ray ray composition (R1-1) for the color filter, it was formed on the substrate. A pixel array of green stripped pixel patterns.

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the unexposed portion of the substrate and no missing portion and scum were observed on the edge of the pixel pattern.

When the section of the pixel pattern was observed via a scanning electron microscope (SEM), no undercut was seen.

Example 3

<Preparation of Liquid Composition and Formation of Colored Layer> A mixture of 15 parts by weight of CI Pigment Blue 15:6/CI Pigment Violet 23 in a weight ratio of 95/5 was treated as a colorant in the same manner as in Example 1. 4 parts by weight (solid content) of Disperbyk-2001 as dispersant, 5 parts by weight of methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenyl maleimide / styrene / copolymer of benzyl methacrylate / glycerol monomethacrylate (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) and 76 parts by weight of propylene glycol Methyl ether acetate was used as a solvent to prepare an initial dispersion (B1).

Thereafter, 100 parts by weight of the initial dispersion (B1) and 6 parts by weight of the polymer-1 (A) synthesized in the above Synthesis Example 1 were designated as the polymer (A) and 9 parts by weight of the dipentaerythritol. Alcohol hexaacrylate as a polyfunctional monomer (C), 0.5 parts by weight of 2-methyl-(4-methylthiophenyl)-2-morpholinel-1-propanone-1 as a photopolymerization initiator ( D), 0.5 parts by weight of A-60 (trade name, Kao Corporation's nonionic surfactant) as an additive, and 150 parts by weight of 3-ethoxypropionate and 25 parts by weight of propylene glycol methyl ether acetate The ester was mixed together as a solvent to prepare a radiation-sensitive composition (B1-1) for use in a color filter.

Thereafter, in the same manner as in Example 1, except that the radiation ray composition (B1-1) for the color filter was used instead of the radiation ray composition (R1-1) for the color filter, it was formed on the substrate. A pixel array of blue stripped pixel patterns.

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the unexposed portion of the substrate and no missing portion and scum were observed on the edge of the pixel pattern.

When the section of the pixel pattern was observed via a scanning electron microscope (SEM), no undercut was seen.

Example 4

<Preparation of Liquid Composition and Formation of Colored Layer> 20 parts by weight of carbon black (manufactured by Mikuni Color Co., Ltd.) as a coloring agent (B) and 2 parts by weight (solid content) of Disperbyk were treated in the same manner as in Example 1. -2001 as dispersant, 4 parts by weight of methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenyl maleimide / styrene / benzyl methacrylate / glycerol mono Copolymer of acrylate (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) and 74 parts by weight of 3-methoxybutyl acetate to prepare initial dispersion (BK1).

Thereafter, 100 parts by weight of the initial dispersion (BK1) and 4.5 parts by weight of the polymer-2 (A) synthesized in the above Synthesis Example 2 were designated as the polymer (A) and 5.5 parts by weight of dipentaerythritol. Alcohol hexaacrylate as polyfunctional monomer (C), 1 part by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone as photopolymerization initiator ( D), 0.5 parts by weight of A-60 (trade name, Kao Corporation's nonionic surfactant) as an additive, and 125 parts by weight of propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone as a solvent are mixed together To prepare a radiation-sensitive composition (BK1-1) for use in a color filter.

Thereafter, in the same manner as in Example 1, except that the radiation ray composition (BK1-1) for the color filter was used instead of the radiation ray composition (R1-1) for the color filter, A pixel array of black stripped pixel patterns.

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the unexposed portion of the substrate and no missing portion and scum were observed on the edge of the pixel pattern.

When the section of the pixel pattern was observed via a scanning electron microscope (SEM), no undercut was seen.

Example 5

<Preparation of Liquid Composition and Formation of Colored Layer> 20 parts by weight of carbon black (manufactured by Mikuni Color Co., Ltd.) as a coloring agent (B) and 2 parts by weight (solid content) of Disperbyk were treated in the same manner as in Example 1. -2001 as dispersant, 4 parts by weight of methacrylic acid, ω-carboxypolycaprolactone monoacrylate, N-phenyl maleimide, styrene, benzyl methacrylate; Copolymer of acrylate (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) and 74 parts by weight of 3-methoxybutyl acetate to prepare initial dispersion (BK2).

Thereafter, 100 parts by weight of the initial dispersion (BK2) and 4.5 parts by weight of the polymer-2 (A) synthesized in the above Synthesis Example 2 were used as the polymer (A) and 5.5 parts by weight of dipentaerythritol. Alcohol hexaacrylate as polyfunctional monomer (C), 1 part by weight of 1-[9-ethyl-6-(2-methylbenzhydryl)-9.H.-carbazol-3-yl] - Ethyl-1-ketooxime-O-acetate as a photopolymerization initiator (D), 0.5 part by weight of A-60 (trade name, Kao Corporation's nonionic surfactant) as an additive, and 125 parts by weight The propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone were mixed together as a solvent to prepare a radiation absorbing composition (BK2-1) for use in a color filter.

Thereafter, in the same manner as in Example 1, except that the radiation ray composition (BK2-1) for the color filter was used instead of the radiation ray composition (R1-1) for the color filter, it was formed on the substrate. A pixel array of black stripped pixel patterns.

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the unexposed portion of the substrate and no missing portion and scum were observed on the edge of the pixel pattern. Further, it is generally confirmed that a finer pixel pattern than Example 4 can be formed and the sensitivity is improved.

When the section of the pixel pattern was observed via a scanning electron microscope (SEM), no undercut was seen.

Claims (5)

A polymer obtained by using (a1) an unsaturated carboxylic acid, (a2) a hydroxyalkyl acrylate and/or a hydroxyalkyl methacrylate, and (a3) selected from the group consisting of aromatic vinyl compounds, anthraquinones, and Saturated carboxylic acid esters, unsaturated carboxylic acid amine alkyl esters, unsaturated carboxylic acid glycidyl esters, vinyl cyanide compounds, unsaturated decylamines, unsaturated quinones, vinyl carboxylates a copolymer of an unsaturated ether, an aliphatic conjugated diene or other unsaturated compound having a mono (meth) acrylonitrile-based macromonomer at the terminal of the polymer molecular chain and selected from the group consisting of isocyanic acid 1,1-(bisacryloxymethyl)ethyl ester, 1,1-(bispropenyloxyethyl)ethyl isocyanate, 1,1-(bispropenyloxypropyl isocyanate) Ethyl ester, 1,1-(bismethylpropenyloxymethyl)ethyl isocyanate, 1,1-(bismethylpropenyloxyethyl)ethyl isocyanate or isocyanate 1 It is obtained by reacting an isocyanate compound of 1-(bismethacryloxypropyl)ethyl ester. A radiation-sensitive composition for use in a color filter comprising (A) a polymer as claimed in claim 1, (B) a colorant, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A radiation ray composition for use in a color filter according to item 2 of the patent application, wherein the polymer (A) according to the first aspect of the patent application has a structure represented by the following formula (2) as derived from the other unsaturated Structure of compound (a3): Wherein R ₃ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. A color filter formed of a radiation-sensitive composition for use in a color filter as in the second or third aspect of the patent application. A liquid crystal display device or panel comprising the color filter of item 4 of the patent application.