JP2008201881A - Alkaline soluble polymer, radiation sensitive composition for forming colored layer, color filter and liquid crystal-displaying element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive composition for forming a colored layer, having a high sensitivity, capable of forming the colored layer excellent in pattern form, residual membrane rate, etc., even in the case of having a low exposure and containing a pigment in a high concentration and also excellent in close adhesion with a substrate plate, and an alkaline soluble polymer containing an unsaturated group, etc., useful as a constituting component of the above composition. <P>SOLUTION: This unsaturated group-containing alkaline soluble polymer is characterized in that its polymer main chain is constituted by a monomer having a polymerizable unsaturated carboxylic acid and/or polymerizable carboxylic acid anhydride as an essential component, and having a (meth)acryloyloxyalkylsilyl group and/or vinylsilyl group as the side chain of the polymer. The radiation sensitive composition for forming the colored layer contains the unsaturated group-containing alkaline soluble polymer, a coloring agent, a polyfunctional monomer and a photoradical-generater. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an unsaturated group-containing alkali-soluble polymer, a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device, and more particularly, a transmissive or reflective color liquid crystal display device, color imaging. Radiation-sensitive composition used for forming a colored layer useful for production of a color filter used for a tube element or the like, a color filter having a colored layer formed from the radiation-sensitive composition, and a liquid crystal provided with the color filter The present invention relates to an unsaturated group-containing alkali-soluble polymer useful as a display element and a component of the radiation-sensitive composition.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing.
In recent years, in the color filter technical field, it has become mainstream to reduce the exposure amount to shorten the tact time. However, in the conventional colored radiation-sensitive composition, if the exposure amount decreases, the residual amount after development is reduced. It is difficult to obtain pixels and black matrix with good pattern shape while shortening the tact time because the film rate is reduced, the pattern is chipped, undercut, and the pattern is easily peeled off from the substrate. .

JP-A-2-144502 JP-A-3-53201

The object of the present invention is a colored layer that is highly sensitive, has excellent pattern shape, residual film ratio, etc., and has excellent adhesion to the substrate, even when it contains a low concentration of light and a high concentration of pigment. It is in providing the radiation sensitive composition for colored layer formation etc. which can form.
Another object of the present invention is to provide a novel alkali-soluble polymer having a reactive unsaturated group in the polymer side chain, which is useful as a component of the radiation-sensitive composition for forming a colored layer.

The present invention, first,
The polymer main chain is composed of a monomer having a polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated carboxylic acid anhydride as an essential component, and a (meth) acryloyloxyalkylsilyl group and / or vinylsilyl is present in the polymer side chain. It comprises an alkali-soluble polymer having a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000 as measured by gel permeation chromatography (GPC).

The present invention secondly,
(A) A radiation-sensitive composition for forming a colored layer, comprising the alkali-soluble polymer, (B) a colorant, (C) a polyfunctional monomer, and (D) a photoradical generator, Consists of. The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

Third, the present invention
The color filter which has a colored layer formed using the said radiation sensitive composition for colored layer formation.

The present invention fourthly,
A liquid crystal display element comprising the color filter.

Hereinafter, the present invention will be described in detail.
Alkali-soluble polymer The alkali-soluble polymer of the present invention has a polymer main chain having a polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated carboxylic acid anhydride (hereinafter, these compounds are collectively referred to as “(a) Unsaturated. Gel permeation chromatography (hereinafter referred to as “carboxylic acid compound”) having a (meth) acryloyloxyalkylsilyl group and / or a vinylsilyl group in the polymer side chain. It consists of an alkali-soluble polymer (hereinafter referred to as “(A) alkali-soluble polymer”) having a polystyrene equivalent weight average molecular weight measured by GPC of 1,000 to 300,000.

  As preferred (A) alkali-soluble polymer in the present invention, for example, (a) an unsaturated carboxylic acid compound and (b) a polymerizable unsaturated compound having one or more hydroxyl groups in one molecule (hereinafter referred to as “ A copolymer of (b) a hydroxyl group-containing unsaturated compound ”) and (c) another polymerizable unsaturated compound (hereinafter referred to as“ copolymer [α] ”) is represented by the following formula (1): The polymer obtained by making the alkoxysilane compound (henceforth "silane compound (1)") represented by these react can be mentioned. Hereinafter, the components (a) to (c) are collectively referred to as “polymerizable unsaturated compound”.

[In the formula (1), X represents a single bond or —OC (═O) — (where the oxygen atom on the left is bonded to Y), and Y represents a single bond when X is a single bond. When X is —OC (═O) —, it represents a methylene group or an optionally substituted alkylene group having 2 to 11 carbon atoms, and each R ¹ is independently a methyl group or a substituted group. And R ² represents a hydrogen atom or a methyl group. However, when both X and Y are single bonds, R ² represents a hydrogen atom. ]

Among the components constituting the copolymer [α], as the (a) unsaturated carboxylic acid compound, for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are commercially available under the trade names of M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively.

Among these (a) unsaturated carboxylic acid compounds, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylphenol, etc. Are preferred, and (meth) acrylic acid is particularly preferred.
In the copolymer [α], (a) unsaturated carboxylic acid compounds can be used alone or in admixture of two or more.

  In the copolymer [α], the content of the repeating unit derived from the (a) unsaturated carboxylic acid compound is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30%. % By weight. In this case, when the content of the repeating unit derived from the (a) unsaturated carboxylic acid compound is less than 5% by weight, the solubility of the polymer obtained by the reaction with the silane compound (1) in the alkaline developer is lowered. On the other hand, if it exceeds 50% by weight, the solubility of the polymer in an alkaline developer may be too high.

Examples of the (b) hydroxyl group-containing unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) (Meth) acrylic acid (poly) such as acrylate, 3,4-dihydroxybutyl (meth) acrylate, 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl (meth) acrylate ) Hydroxyalkyl Esters and 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-2- hydroxyethyl (meth) acrylamide.
Among these (b) hydroxyl group-containing unsaturated compounds, 2-hydroxyethyl (meth) acrylate and 1,2-dihydroxyethyl (meth) acrylate from the viewpoint of copolymerization reactivity and reactivity with the silane compound (1). 2,3-dihydroxypropyl (meth) acrylate and the like are preferable.
In the copolymer [α], the hydroxyl group-containing unsaturated compound (b) can be used alone or in admixture of two or more.

  In the copolymer [α], the content of the repeating unit derived from the (b) hydroxyl group-containing unsaturated compound is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight. %. In this case, when the content of the repeating unit derived from the (b) hydroxyl group-containing unsaturated compound is less than 1% by weight, the rate of introduction of the silane compound (1) into the polymer is lowered to obtain a radiation-sensitive composition. When the amount exceeds 50% by weight, the storage stability of the polymer obtained by the reaction with the silane compound (1) tends to decrease.

Moreover, as (c) other polymerizable unsaturated compounds, for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, Soboruniru (meth) acrylate, unsaturated carboxylic acid esters such as dicyclopentadienyl (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide and α-chloroacrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

Among these (c) other polymerizable unsaturated compounds, styrene, methyl (meth) acrylate, n-propyl (meth) acrylate are used from the viewpoint of copolymerization reactivity and solubility of the resulting polymer in an alkaline developer. I-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide and the like are preferable.
In the copolymer [α], (c) other polymerizable unsaturated compounds may be used alone or in admixture of two or more.

  In the copolymer [α], the content of the repeating unit derived from (c) another polymerizable unsaturated compound is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, and particularly preferably 30 to 30%. 50% by weight. In this case, when the content of the repeating unit derived from (c) another polymerizable unsaturated compound is less than 10% by weight, the storage stability of the polymer obtained by the reaction with the silane compound (1) tends to decrease. On the other hand, if it exceeds 70% by weight, the solubility of the polymer in an alkaline developer tends to decrease.

  Preferred copolymers [α] in the present invention include, for example, (a) an unsaturated carboxylic acid compound having (meth) acrylic acid as an essential component, 2-hydroxyethyl (meth) acrylate, and 1,2-dihydroxy. (B) a hydroxyl group-containing unsaturated compound having at least one selected from the group of ethyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate as an essential component, styrene, methyl (meth) acrylate, and n-propyl (Meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate and at least one selected from the group of N-phenylmaleimide (c ) Copolymers [α] with other unsaturated compounds can be mentioned,

More specifically,
(A) unsaturated carboxylic acid-based compound having (meth) acrylic acid as an essential component, (b) hydroxyl group-containing unsaturated compound having 2-hydroxyethyl (meth) acrylate as an essential component, styrene, methyl (meth) At least selected from the group of acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate and N-phenylmaleimide One (c) copolymer with other unsaturated compounds [α];

(A) an unsaturated carboxylic acid compound having (meth) acrylic acid as an essential component, (b) a hydroxyl group-containing unsaturated compound having 1,2-dihydroxyethyl (meth) acrylate as an essential component, styrene, methyl ( Selected from the group of (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate and N-phenylmaleimide A copolymer [α] with at least one (c) other unsaturated compound,

(A) an unsaturated carboxylic acid compound having (meth) acrylic acid as an essential component, (b) a hydroxyl group-containing unsaturated compound having 2,3-dihydroxypropyl (meth) acrylate as an essential component, styrene, methyl ( Selected from the group of (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate and N-phenylmaleimide A copolymer with at least one (c) other unsaturated compound [α]
Etc.

The copolymer [α] can be produced, for example, by polymerizing a polymerizable unsaturated compound in an appropriate solvent in the presence of a radical polymerization initiator.
As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, 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, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;

Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, 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, propylene glycol mono-n-butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, methoxyacetic acid -Propyl, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyloxyacetate n-propyl, n -Other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetate, n-butyloxybutoxyacetate, and the like.
Of these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

In addition, the radical polymerization initiator is not particularly limited. For example, 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′-azobis (2-methylpropionate), Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, etc. And organic peroxides such as hydrogen peroxide.
Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox initiator by using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer [α] in the present invention is 1,000 to 300,000, Preferably it is 5,000-100,000.
In addition, the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer [α] in the present invention is usually from 3,000 to 3,000. 60,000, preferably 5,000 to 25,000.
In this case, if the Mw of the copolymer [α] is less than 3,000, alkali developability, residual film ratio, heat resistance, pattern shape and the like when used as a radiation sensitive composition tend to decrease, On the other hand, if it exceeds 300,000, the resolution, pattern shape, etc. when used as a radiation-sensitive composition tend to decrease.

The copolymer [α] can also be produced by subjecting a polymerizable unsaturated compound to living radical polymerization in a solvent in the presence of a radical polymerization initiator system that generates a living radical.
In the living radical polymerization, when the polymerizable unsaturated compound contains a compound having a functional group that may deactivate the living radical, such as a carboxyl group, it is necessary to prevent the growth terminal from being deactivated. Accordingly, the functional group in the polymerizable unsaturated compound is protected and polymerized by, for example, esterification, and then deprotected, whereby the copolymer [α] can be obtained.

  Various radical polymerization initiator systems used for living radical polymerization have been proposed. For example, the TEMPO system proposed by Georges et al. A system composed of a combination of copper chloride and a bromine-containing ester compound (for example, see Non-patent Document 2), a system composed of a combination of carbon tetrachloride and a ruthenium (II) complex proposed by Hamasaki et al. 3), and a system comprising a combination of a thiocarbonyl compound having a chain transfer constant greater than 0.1 and a radical initiator, as disclosed in Patent Document 3, Patent Document 4 and Patent Document 5. be able to.

M.K.Georges, R.P.N.Veregin, P.M.Kazmaier, G.K.Hamer, Macromolecules, 1993, Vol.26, p.2987 Matyjaszewski, K. Coca, S. Gaynor, G. wei, M. Woodworth, B.E. Macromolecules, 1997, Vol. 30, p. 7348 Hamasaki, S.Kamigaito, M.Sawamoto, M. Macromolecules, 2002, Vol.35, p.2934 Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181) Special Table 2002-2002 JP-T-2004-518773

As a suitable radical polymerization initiator system used in the living radical polymerization, a system in which the living radical at the growth end is not deactivated is appropriately selected according to the type of the polymerizable unsaturated compound used. In consideration of efficiency, metal-free system, etc., a combination of a thiocarbonylthio compound that is a molecular weight control agent and a radical initiator is preferable.
The combination of the thiocarbonylthio compound and the radical initiator is described in detail in the following patent documents in addition to the patent documents 3 to 5.

Special table 2002-508409 gazette Japanese translation of PCT publication No. 2002-512653 Special table 2003-527458 gazette Patent 3634843 (Japanese Patent Publication No. 2003-536105) JP-T-2005-503452

  As described in Patent Documents 3 to 6, a random copolymer or a block copolymer having a narrow molecular weight distribution is obtained by living radical polymerization of a polymerizable unsaturated compound in the presence of a thiocarbonylthio compound and a radical initiator. Coalescence can be obtained. Moreover, since the functional group derived from a thiocarbonylthio compound can be introduce | transduced into the obtained random copolymer and block copolymer, this copolymer is made into aqueous gel (refer patent document 7), photoresist ( It has been clarified that it can also be used for applications such as a surfactant (see Patent Document 8) and a surfactant (see Patent Document 9).

  In the present invention, as a typical copolymer [α] produced by living radical polymerization, at least one terminal of each polymer chain constituting the group is represented by a group represented by the following formula (i) (hereinafter, (Hereinafter referred to as “terminal group (i)”) or a group represented by formula (ii) (hereinafter referred to as “terminal group (ii)”) (hereinafter referred to as “thiocarbonylthio-terminated copolymer [ α] ”)).

[In Formula (i), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. A monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OR, -SR, -N (R) ₂ ,
-OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ , -P (= O) (R) _2, or 1 represents a monovalent group having a polymer chain, and each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 18 carbon atoms. A monovalent heterocyclic group having 3 to 18 total atoms of a group or a carbon atom and a hetero atom, the above-mentioned alkyl group having 1 to 20 carbon atoms, and a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms The group, the monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted. ]

[In the formula (ii), Z ² represents an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and a hetero atom. A m-valent group derived from a heterocyclic compound having a total of 3 to 20 atoms or an m-valent group having a polymer chain, an m-valent group derived from the alkane having 1 to 20 carbon atoms, the number of carbon atoms The m-valent group derived from 6 to 20 aromatic hydrocarbons and the m-valent group derived from the heterocyclic compound having 3 to 20 atoms in total may be substituted, and m is an integer of 2 or more. is there. ]

When the thiocarbonylthio-terminated copolymer [α] has only one polymer chain, the terminal group (i) is usually bonded to one end of the polymer chain, while the other A terminal group (i), a terminal group (ii), or a chain terminating group may be bonded to the terminal of. This “chain terminating group” is a group determined by the reaction conditions during living radical polymerization. When the terminal group (ii) is bonded to the polymer chain, it is bonded to the polymer chain in the terminal group (ii). (M-1) bonds (S-) which are not bonded to the chain terminating group. The chain terminating group may be R ³ in formula (2) described later or R ⁴ in formula (3) described later.
In addition, when there are two or more polymer chains constituting it, each polymer chain is usually bonded to the terminal group (ii) at one end thereof, and the copolymer (I) has a branched structure. Thus, a terminal group (i), a terminal group (ii) or a chain terminating group can be bonded to the other terminal of each polymer chain. And when the said terminal group (ii) couple | bonds with the other terminal of a polymer chain, (m-1) bond (S-) which is not couple | bonded with the polymer chain in this terminal group (ii). ) May be further bonded to a terminal group (i), a terminal group (ii) or a chain terminating group. The chain terminating group may be R ³ in formula (2) described later or R ⁴ in formula (3) described later.

In the formula (i), Z ¹ of the optionally substituted alkyl group having 1 to 20 carbon atoms, substituted 1 also show good C6-20 optionally monovalent aromatic hydrocarbon group, optionally substituted Preferred examples of the monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, optionally substituted R, and a monovalent group having a polymer chain are also preferred. In addition, for example, the same groups as those corresponding to each of Z ¹ in formula (2) described later can be exemplified.

In the formula (ii), m 2 derived from an alkane having 1 to 20 carbon atoms which may be substituted in Z ² , m derived from an aromatic hydrocarbon having 6 to 20 carbon atoms which may be substituted. As a valent group, an m-valent group derived from a heterocyclic compound having 3 to 20 total atoms of carbon atoms and hetero atoms, which may be substituted, and an m-valent group having a polymer chain, Including those preferred ones, for example, the same groups as those corresponding to each of Z ² in formula (3) described later can be exemplified.

  The thiocarbonylthio-terminated copolymer [α] is, for example, a step of living radical polymerization of a polymerizable unsaturated compound using a thiocarbonylthio compound represented by the following formula (2) or formula (3) as a molecular weight control agent. In this living radical polymerization, a radical initiator is usually also used.

[In the formula (2), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. A monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OR, -SR, -N (R) ₂ ,
-OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ , -P (= O) (R) _2, or 1 represents a monovalent group having a polymer chain, and each R is independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 18 carbon atoms. A monovalent heterocyclic group having 3 to 18 total atoms of a group or a carbon atom and a hetero atom, and the aforementioned alkyl group having 1 to 20 carbon atoms and a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms Group, monovalent heterocyclic group having 3 to 20 atoms in total and R may each be substituted, p is an integer of 1 or more, and R ³ is 1 to 1 carbon atoms when p = 1. 20 alkyl groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 3 to 20 total atoms of carbon atoms and hetero atoms 1 of Heterocyclic group, -OR, -SR, represent a monovalent group having a -N (R) ₂ or a polymer chain, each R is an alkyl group having 1 to 18 carbon atoms independently of one another, carbon atoms 2 -18 alkenyl group, monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and hetero atoms, p = 2 A single bond, a divalent group derived from an alkane having 1 to 20 carbon atoms, a divalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a total number of atoms of carbon atoms and hetero atoms of 3 A divalent group derived from a heterocyclic compound having ˜20 or a divalent group having a polymer chain, and when p ≧ 3, a p-valent group derived from an alkane having 1 to 20 carbon atoms, the number of carbons P-valent group derived from 6-20 aromatic hydrocarbons, derived from a heterocyclic compound having a total of 3-20 carbon atoms and hetero atoms 1 represents a p-valent group or a p-valent group having a polymer chain, the alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 1 having 6 to 20 carbon atoms. Valent aromatic hydrocarbon group, monovalent heterocyclic group having 3 to 20 atoms in total, R, divalent group derived from alkane having 1 to 20 carbon atoms, aromatic hydrocarbon having 6 to 20 carbon atoms A divalent group derived from a divalent group derived from a heterocyclic compound having 3 to 20 atoms in total, a p-valent group derived from an alkane having 1 to 20 carbon atoms, an aromatic having 6 to 20 carbon atoms A p-valent group derived from a hydrocarbon and a p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted. ]

[In the formula (3), Z ² represents an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and a hetero atom. M-valent group derived from a heterocyclic compound having a total of 3 to 20 atoms or m-valent group having a polymer chain, m-valent group derived from the alkane having 1 to 20 carbon atoms, carbon number The m-valent group derived from an aromatic hydrocarbon having 6 to 20 and the m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted, and R ⁴ may have 1 to 1 carbon atoms. 20 alkyl groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 3 to 20 total atoms of carbon atoms and hetero atoms A monovalent heterocyclic group, —OR, —SR, —N (R) ₂ or a monovalent group having a polymer chain, wherein each R is mutually Independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 18 atoms of carbon atoms and hetero atoms 1 represents a monovalent heterocyclic group, the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. , A monovalent heterocyclic group having 3 to 20 atoms in total and R may each be substituted, and m is an integer of 2 or more. ]

In the formula (2), examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, sec- Butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3-dimethyl A butyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of Z ¹ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 9-anthracenyl group, a benzyl group, An α-methylbenzyl group, an α, α-dimethylbenzyl group, a phenethyl group, and the like can be given.

Examples of the monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms of Z ¹ include oxiranyl group, aziridinyl group, 2-furanyl group, 3-furanyl group, 2- Tetrahydrofuranyl group, 3-tetrahydrofuranyl group, 1-pyrrole group, 2-pyrrole group, 3-pyrrole group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-pyrazole group, 2-pyrazole group, 3-pyrazole group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-thianyl group, 3-thianyl group, 4-thianyl group, 2-pyridinyl group, 3-pyridinyl group 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group, etc. Can.

Z ¹ —OR, —SR, —N (R) ₂ , —OC (═O) R, —C (═O) OR,
An alkyl group having 1 to 18 carbon atoms of R in —C (═O) N (R) ₂ , —P (═O) (OR) ₂ and —P (═O) (R) ₂ ; As the monovalent aromatic hydrocarbon group or the monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and hetero atoms, for example, an alkyl group having 1 to 20 carbon atoms exemplified for Z ¹ Among monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms or monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, the number of carbon atoms or the total number of atoms is 18 or less. Can be mentioned.
Examples of the alkenyl group having 2 to 18 carbon atoms of the same R include, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.

For the alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, and R Examples of the substituent include, for example, hydroxyl group, carboxyl group, carboxylate group, sulfonate group, sulfonate group, isocyanate group, cyano group, vinyl group, epoxy group, silyl group, halogen atom, and Z ¹ . -OR, -SR, -N (R) ₂ , -OC (= O) R,
-C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ or -P (= O) (R) _2, or carbon number exemplified for R 1 -18 alkyl group, alkenyl group having 2 to 18 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or monovalent heterocyclic ring having 3 to 18 total atoms of carbon atoms and hetero atoms A group similar to the formula group can be selected as appropriate, and one or more of these substituents can be present in the substituted derivative. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the monovalent group having a polymer chain of Z ¹ include α-olefins such as ethylene and propylene; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl fluoride, vinyl chloride, and chloride. Vinyl halides such as vinylidene; unsaturated alcohols such as vinyl alcohol and allyl alcohol; esters of unsaturated alcohols such as vinyl acetate and allyl acetate; unsaturated carboxylic acids such as (meth) acrylic acid and p-vinylbenzoic acid Acids; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t- (meth) acrylic acid (Meth) acrylic acid esters such as butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate; (Meth) acrylamides such as Acrylamide and N, N-dimethyl (meth) acramide; Unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; One kind of unsaturated compounds such as conjugated dienes such as butadiene and isoprene In addition to the monovalent group having an addition polymerization polymer chain formed as described above, a polyoxyethylene whose terminal may be etherified, a polyether such as polyoxypropylene whose terminal may be etherified, And monovalent groups having a polyaddition polymer chain such as polyester, polyamide, or polyimide, or a polycondensation polymer chain. In the monovalent group having these polymer chains, even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (6), for example, —CH ₂ —COO—, —C (CH ₃₎ (CN) may be through a linking hand CH ₂ CH ₂ -COO-, etc. attached to the carbon atom of the thiocarbonyl group in the formula (1).
In Formula (2), a plurality of Z ¹ may be the same or different from each other.

In Formula (2), when p = 1, R ³ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent group having 6 to 20 carbon atoms. A monovalent heterocyclic group having a total of 3 to 20 atoms of carbon atoms and hetero atoms, —OR, —SR, —N (R) ₂ or a monovalent polymer chain. A group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon atom different from the above. The monovalent heterocyclic group having 3 to 20 atoms in total and R may each be substituted.
The alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -SR, -N (R As the monovalent group having ₂ or a substituted derivative or polymer chain thereof, for example, the same groups as those exemplified for the respective groups corresponding to Z ¹ can be mentioned. In a monovalent group having a polymer chain of R ³ (p = 1), even when the polymer chain is directly bonded to the sulfur atom in the formula (2), for example, —CH ₂ —COO— , —C (CH ₃ ) (CN) CH ₂ CH ₂ —COO— or the like, may be bonded to the sulfur atom in the formula (2) through a connecting hand.

Moreover, as said C3-C20 monovalent alicyclic hydrocarbon group, a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, a cyclohexenyl group etc. can be mentioned, for example.
Examples of the substituent for the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms in Z ^{1 and} a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. Group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom, and a group similar to those exemplified for the substituent for R can be appropriately selected from these substituents. May be present in the substituted derivative in one or more or one or more. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

When p = 2, R ³ is a single bond, a divalent group derived from an alkane having 1 to 20 carbon atoms, a divalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, or a carbon atom. A divalent group derived from a heterocyclic compound having a total number of atoms of 3 to 20 and a divalent group having a polymer chain, and a divalent group derived from the alkane having 1 to 20 carbon atoms , A divalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms and a divalent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted.

Further, when p ≧ 3, R ³ is a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, or a carbon atom different from that of carbon atoms. A p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or a p-valent group having a polymer chain, and derived from a p-valent group derived from the alkane or an aromatic hydrocarbon The p-valent group and the p-valent group derived from the heterocyclic compound having 3 to 20 atoms in total may be substituted.

  Examples of the alkane having 1 to 20 carbon atoms include methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, n-octane, and n. -Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane and the like can be mentioned.

Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include benzene and 1,4-dimethylbenzene (for example, a carbon atom of each methyl group at the 1,4-position is a sulfur atom in the formula (2)). ), 1,2,4,5-tetramethylbenzene (for example, the carbon atom of each methyl group at the 1,2,4,5-position binds to the sulfur atom in formula (2).) 1,2,3,4,5,6-hexamethylbenzene (for example, the carbon atom of each methyl group at the 1,2,3,4,5,6-position binds to the sulfur atom in formula (2)) And 1,4-di-i-propylbenzene (for example, the 2-position carbon atom of each i-propyl group at the 1,4-position is bonded to the sulfur atom in formula (2)). Naphthalene, anthracene group and the like can be mentioned.
Examples of the heterocyclic compound having 3 to 20 atoms in total include oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thiane, pyridine, piperidine, morpholine, and the like.

A divalent group derived from the alkane having 1 to 20 carbon atoms, a divalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a divalent group derived from a heterocyclic compound having 3 to 20 atoms in total. A p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound having 3 to 20 atoms in total. Examples of the substituent for the p valent group, for example, an alkyl group having 1 to 20 carbon atoms of the Z ^1, 1 monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the total atoms of carbon atoms and hetero atoms The monovalent heterocyclic group of 3 to 20 and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are one or more or one or more in the substituted derivatives. Can exist. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the polymer chain that gives the divalent group of R ^{3 and} the polymer chain that gives the p-valent group include addition polymerization polymers exemplified for the monovalent group having the Z ¹ polymer chain. Examples thereof include the same chain, polyaddition polymer chain and polycondensation polymer chain. In the case of a divalent group having a polymer chain of R ³ and a p-valent group, even if the polymer chain is directly bonded to the sulfur atom in the formula (2), for example, —CH ₂ —COO—, — C (CH ₃₎ (CN) may be through a linking hand CH ₂ CH ₂ -COO-, etc. attached to the sulfur atom in the formula (2).

Next, in the formula (3), examples of the alkane having 1 to 20 carbon atoms that give an m-valent group of Z ² include, for example, 1 to 20 carbon atoms that give a divalent group and a p-valent group of R ^3. The same compounds as those exemplified for the alkane can be exemplified.
Further, examples of the aromatic hydrocarbon having 6 to 20 carbon atoms that give an m-valent group of Z ² include, for example, an aromatic carbon atom having 6 to 20 carbon atoms that gives a divalent group of R ³ and a p-valent group. The thing similar to the compound illustrated about hydrogen can be mentioned.
Further, examples of the heterocyclic compound having a total of 3 to 20 carbon atoms and hetero atoms of the Z ² m-valent group include the R ³ divalent group and p-valent group. The thing similar to the compound illustrated about the heterocyclic compound of 3-30 total atoms of a carbon atom and a hetero atom can be mentioned.

Derived from an m-valent group derived from an alkane having 1 to 20 carbon atoms of Z ² , an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound having 3 to 20 atoms in total. Examples of the substituent for the m-valent group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total atom of carbon atoms and hetero atoms. The monovalent heterocyclic group of 3 to 20 and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are one or more or one or more in the substituted derivatives. Can exist. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the polymer chain that gives an m-valent group of Z ² include, for example, the addition polymerization-type polymer chain, polyaddition-type polymer chain, and heavy chain exemplified for the monovalent group having the Z ¹ polymer chain. The thing similar to a condensation type polymer chain can be mentioned. In the m-valent group having a polymer chain of Z ² , even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (3), for example,
_{-CH 2 -COO -, - C (} CH 3) (CN) may be through a linking hand CH ₂ CH ₂ -COO-, etc. attached to the carbon atom of the thiocarbonyl group in the formula (3).

In the formula (3), R ⁴ alkyl group having 1 to 20 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent having 3 to 20 total atoms of carbon atoms and hetero atoms. As the monovalent group having a heterocyclic group, —OR, —SR, —N (R) ₂ and a polymer chain, or a substituted derivative thereof, for example, groups exemplified for the corresponding groups of Z ¹ The same thing can be mentioned. In the monovalent group having a polymer chain of R ⁴ , even when the polymer chain is directly bonded to the sulfur atom in the formula (3), for example, —CH ₂ —COO—,
-C (CH ₃₎ (CN) may be through a linking hand CH ₂ CH ₂ -COO-, etc. attached to the sulfur atom in the formula (3).
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ⁴ and substituted derivatives thereof include, for example, monovalent fats having 3 to 20 carbon atoms of the above R ³ (p = 1). The thing similar to the group illustrated about the cyclic hydrocarbon group and its substituted derivative can be mentioned.
In the formula (3), a plurality of R ⁴ may be the same or different from each other.
In Formula (3), when the connecting part between Z ² and —C (═S) —S—R ⁴ is an aliphatic carbon atom, the aliphatic carbon atom in Z ² is —C (═S ) When bonded to —S—R ⁴ and the linking moiety is an aromatic carbon atom, the aromatic carbon atom in Z ² is bonded to —C (═S) —S—R ^4, and When the moiety is a sulfur atom, the sulfur atom in —SR representing Z ² is bonded to —C (═S) —S—R ⁴ .

  Specific examples of particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (4) to (23).

These thiocarbonylthio compounds can be used alone or in admixture of two or more.
In the present invention, at the time of living radical polymerization, one or more kinds of other molecular weight control agents such as α-methylstyrene dimer and t-dodecyl mercaptan can be used in combination with the thiocarbonylthio compound.
The radical initiator used in the living radical polymerization is not particularly limited, and those generally known as radical polymerization initiators can be used. For example, the copolymer [α] can be produced. Examples of the radical polymerization initiator exemplified for the radical polymerization are as follows.
These radical initiators can be used alone or in admixture of two or more.

The solvent used in the living radical polymerization is not particularly limited as long as the living radical is not deactivated.
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, etc. Poly) alkylene glycol alkyl ether acetates;
(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether;
Other ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one, etc. Keto alcohols;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, ethyl ethoxy acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as Le;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, from the viewpoints of solubility of each component, pigment dispersibility, coatability and the like when a liquid composition of a radiation sensitive resin composition described later is used. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate Acetate n- butyl acetate i- butyl, formic acid n- pentyl acetate, i- pentyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

In the living radical polymerization, the amount of the thiocarbonylthio compound used is usually 0.1 to 50 parts by weight, preferably 0.2 to 16 parts by weight, based on 100 parts by weight of the polymerizable unsaturated compound. The usage-amount of an initiator is 0.1-50 weight part normally with respect to 100 weight part of polymerizable unsaturated compounds, Preferably it is 0.1-20 weight part.
The polymerization temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and the polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

Furthermore, the copolymer [α] can be obtained by polymerizing a polymerizable unsaturated compound in the presence of a radical polymerization initiator and then purifying it through a reprecipitation method using two or more organic solvents having different polarities. Can do.
The radical polymerization for producing a copolymer to be subjected to purification (hereinafter referred to as “unpurified copolymer”) is not particularly limited. For example, the copolymer [α] can be prepared by a conventional method. It can be carried out in the same manner as radical polymerization in production.
If the solvent used for the polymerization is a good solvent in the reprecipitation method described below, the unpurified copolymer after polymerization can be subjected to purification treatment as a polymer solution as it is or after adjusting the concentration. The unpurified copolymer can be separated from the polymer solution obtained by polymerization by a conventional method and subjected to purification treatment as a solid.

After polymerization, the resulting unpurified copolymer is purified by a reprecipitation method using two or more organic solvents having different polarities. That is, after removing the insoluble impurities from the solution of the unpurified copolymer in a good solvent by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution) is precipitated. It refine | purifies by pouring in an agent (poor solvent) and reprecipitating a copolymer. At that time, of the impurities remaining in the polymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified copolymer [α].
Examples of the good solvent / precipitant combination used in this reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, and methyl ethyl ketone / n-heptane. Can be mentioned.

  During reprecipitation of the unpurified copolymer, it is desirable to add the polymer solution as little as possible while vigorously stirring the precipitant, thereby minimizing the amount of impurities incorporated into the precipitate. Moreover, the purity of copolymer [(alpha)] can be made higher by repeating a reprecipitation process in multiple times. If the precipitated copolymer [α] is very fine and not suitable for filtration, it can be separated by centrifugation or the like.

Further, when more rigorous purification is required, a fractional precipitation method that is a modified method of the reprecipitation method is desirable. That is, the purified copolymer is dissolved by dissolving the unpurified copolymer in a good solvent and sequentially precipitating the unpurified copolymer as a solute while finely changing the solvent conditions (solvent type, composition and temperature). The polymer [α] is divided into a plurality of sections having slightly different solubility. In this method, it is common to add a precipitant to the polymer solution. Further, the composition of the good solvent and the precipitating agent (mixing ratio of the good solvent) may be sequentially changed at a constant temperature, or the temperature may be changed while keeping the mixing ratio of the good solvent constant. By using such a fractional precipitation method, the copolymer [α] in a narrow molecular weight range can be fractionated with a high yield. Each fraction of the copolymer [α] fractionated by the fractional precipitation method can be obtained as a solid by concentrating and drying one or more fractions according to their Mw values. it can.
Furthermore, the copolymer [α] obtained by such a reprecipitation method can be further purified by adsorption / affinity chromatography, dialysis method or the like, if necessary.

The Mw of the copolymer [α] obtained by the living radical polymerization or reprecipitation method is preferably 1,000 to 45,000, more preferably 3,000 to 20,000, particularly preferably 4,000 to 10,000. 000.
Further, the ratio (Mw) of the copolymer [α] obtained by living radical polymerization or reprecipitation method to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) ( Mw / Mn) is preferably 1.0 to 2.0, more preferably 1.0 to 1.7, and particularly preferably 1.0 to 1.4.
The copolymer [α] thus obtained may be used in the production of the (A) alkali-soluble polymer as it is in the polymerization solution, or once separated from the solution (A) the alkali-soluble polymer. You may use for manufacture of.

  By reacting the silane compound (1) with the copolymer [α] thus obtained, (A) an alkali-soluble polymer can be obtained.

In the formula (1), examples of the alkylene group having 2 to 11 main chain carbon atoms of Y include 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, and 1,3-butylene. Group, 2-methyl-1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,7-heptylene group, 1,8-octylene group, 1, A 9-nonylene group, a 1,10-decylene group, a 1,11-undecylene group, and the like can be given.
Examples of the substituent for the alkylene group include a halogen atom (eg, fluorine atom, chlorine atom) and an alkoxyl group (eg, methoxy group, ethoxy group).

  In the formula (1), Y is preferably an alkylene group having 3 or 4 main chain carbon atoms, and particularly preferably a 1,3-propylene group.

In the formula (1), examples of the substituent for the ethyl group of R ¹ include a halogen atom (eg, fluorine atom, chlorine atom), an alkoxyl group (eg, methoxy group, ethoxy group, etc.) and the like. Can do.

In the present invention, specific examples of the particularly preferred silane compound (1) include
Acryloyl group-containing compounds such as 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylethoxydimethoxysilane, 3-acryloyloxypropylmethoxydiethoxysilane, 3-acryloyloxypropyltriethoxysilane; 3-methacryloyloxypropyltrimethoxy Methacryloyl group-containing compounds such as silane, 3-methacryloyloxypropylethoxydimethoxysilane, 3-methacryloyloxypropylmethoxydiethoxysilane, 3-methacryloyloxypropyltriethoxysilane;
Vinyltrimethoxysilane, vinylethoxydimethoxysilane, vinylmethoxydiethoxysilane, vinyltriethoxysilane, vinyl (2-methoxyethoxy) diethoxysilane, vinylethoxybis (2-methoxyethoxy) silane, vinyltris (2-methoxyethoxy) Examples include vinyl group-containing compounds such as silane.

  Of these silane compounds (1), 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and the like are preferable from the viewpoint of reactivity with the copolymer [α]. Examples of commercially available products of 3-methacryloyloxypropyltrimethoxysilane include, for example, Silaace S710 (manufactured by Chisso Corporation) under the trade name.

In the reaction of the copolymer [α] with the silane compound (1), the silane compound (1) can be used alone or in admixture of two or more.
In the present invention, the reaction between the copolymer [α] and the silane compound (1) is performed by adding the silane compound (1) to the solution of the copolymer [α] while stirring at room temperature or under heating. Can be implemented.

  (A) The amount of the silane compound (1) used in producing the alkali-soluble polymer is preferably relative to the amount of the (b) hydroxyl group-containing unsaturated compound used in the synthesis of the copolymer [α]. Is 0.1 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 25 to 75% by weight. In this case, if the amount of the silane compound (1) used is less than 0.1% by weight, the effect of improving the sensitivity and elastic properties when used as a radiation-sensitive composition tends to be small, whereas if it exceeds 90% by weight. The unreacted silane compound (1) remains, and the storage stability of the resulting reaction solution and the liquid composition described later may be reduced.

  In the reaction between the copolymer [α] and the silane compound (1), the hydroxyl group in the copolymer [α] reacts with the methoxy group or the (substituted) ethoxy group in the silane compound (1) to form (meta ) An acryloyloxyalkyl group and / or a vinyl group is introduced into the polymer side chain via a siloxane bond. In this case, the number of (meth) acryloyloxyalkyl groups and / or vinyl groups introduced into the alkali-soluble polymer per molecule of the polymer is naturally the number of the silane compound (1) used. It depends on the amount. In addition, since all three methoxy groups or (substituted) ethoxy groups in the silane compound (1) have reactivity with the hydroxyl groups in the copolymer [α], the bonding form of the siloxane bond is From the case where only one methoxy group or (substituted) ethoxy group reacts to the case where all three react, and when two methoxy groups or (substituted) ethoxy groups react, in general, the bridge structure is When three methoxy groups or (substituted) ethoxy groups are reacted with each other, a crosslinked structure or a crosslinked structure is generally formed, and usually a bonded form of these siloxane bonds is obtained (A). This results in mixing in the alkali-soluble polymer.

  (A) The alkali-soluble polymer has a carboxyl group and / or a carboxylic acid anhydride group and a reactive (meth) acryloyl group and / or a vinyl group, and is appropriately dissolved in an alkali developer. In addition, it can be easily cured by heating without using a special curing agent, and it can be used particularly suitably for the formation of colored layers (pixels and black matrix) in color filters. In addition, it is useful as a constituent component of a protective film for a liquid crystal display element, an interlayer insulating film, a spacer for a liquid crystal display element, a microlens, a paint, an adhesive, and the like utilizing the reactivity.

Radiation-sensitive composition for forming colored layer The radiation-sensitive composition for forming a colored layer of the present invention comprises (A) an alkali-soluble polymer, (B) a colorant, (C) a polyfunctional monomer, and (D). It contains a photo radical generator.
In the present invention, as the alkali-soluble resin component, other alkali-soluble polymers can be used in combination with (A) the alkali-soluble polymer.
The other alkali-soluble polymer is not particularly limited, and for example, (a) at least one selected from the group of unsaturated carboxylic acid compounds and (b) a hydroxyl group-containing unsaturated compound and (C) A copolymer with at least one selected from the group of other polymerizable unsaturated compounds can be mentioned.

As specific examples of other alkali-soluble polymers,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl (meth) acrylate,
(Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-cyclohexylmaleimide / α-methylstyrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / styrene / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / styrene / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / 2,3-dihydroxypropyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / 2,3-dihydroxypropyl (meth) acrylate copolymer.
These other alkali-soluble polymers can be used alone or in admixture of two or more.

In the present invention, the total amount of (A) alkali-soluble polymer and other alkali-soluble polymer used is usually 10 to 1,000 parts by weight, preferably 20 parts per 100 parts by weight of (B) colorant. -500 parts by weight. In this case, if the total amount used is less than 10 parts by weight, for example, alkali developability may be deteriorated, or background contamination or film residue may be generated on the substrate in the unexposed area or on the light shielding layer. If it exceeds 000 parts by weight, the colorant concentration is relatively lowered, so that it may be difficult to achieve the target color density as a thin film.
In addition, when (A) an alkali-soluble polymer and another alkali-soluble polymer are used in combination, the proportion of (A) alkali-soluble polymer used is preferably 50 to 100% by weight based on the total of both polymers. More preferably, it is 80 to 100% by weight, and particularly preferably 90 to 100% by weight. In this case, if the usage ratio is less than 50% by weight, chipping of the pattern edge or undercut may occur in the case of a low exposure amount.

-(B) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Organic pigments or inorganic pigments are used, and organic pigments and carbon black are particularly preferably used.
Examples of the organic pigment include a color index (CI; The Society of Dyers).
and Colorists (published by and Colorists)), specifically, compounds having a color index (CI) number as shown below.

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 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 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment ...... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175, C.I Pigment Yellow 180, C.I 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, 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, 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 Pigment 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 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 pigmentless 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 150, 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, C.I. Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60;
CI Pigment Green 7, CI Pigment Green 36;
CI Pigment Brown 23, CI Pigment Brown 25;
CI Pigment Black 1, CI Pigment Black 7.
These organic pigments can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

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

In the present invention, the organic pigment and the inorganic pigment can be used alone or in combination of two or more, and the organic pigment and the inorganic pigment can be used together. Preferably, one or more organic pigments are used, and when forming the black matrix, two or more organic pigments and / or carbon black are preferably used.
In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymer described in Patent Document 11 and various commercially available polymers or oligomers for dispersing pigments.
JP-A-8-259876

Moreover, in this invention, a coloring agent can be used with a dispersing agent depending on necessity. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl Polyoxyethylene alkyl phenyl ethers such as 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; Polyethyleneimines In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). Megafuck (Dainippon Ink and Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Dispersbyk (Bicchemy Japan), Solsparse (Seneca Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.

  In the present invention, the radiation-sensitive composition for forming a colored layer can be prepared by an appropriate method. When a pigment is used as a colorant, the pigment is used in a solvent in the presence of a dispersant, for example, a bead mill, Using a roll mill or the like, mixing and dispersing while pulverizing to obtain a pigment dispersion, comprising this as component (A), component (C) and component (D), additional solvents as necessary, and others described below It is preferable to prepare by adding and mixing the additives.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly 100 parts by weight of the pigment. The amount is preferably 10 to 50 parts by weight. In this case, if the amount of the dispersant used exceeds 100 parts by weight, developability and the like may be impaired.
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent illustrated about the liquid composition of the radiation sensitive composition mentioned later can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is usually 200 to 1,200 parts by weight, preferably 300 to 1,000 parts by weight with respect to 100 parts by weight of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture composed of a pigment, a solvent and a dispersant is used. Preferably, it can be carried out by mixing and dispersing while cooling with water or the like.
In this case, the filling rate of the beads is usually 50 to 80% of the mill capacity, and the injection amount of the pigment mixture is usually about 20 to 50% of the mill capacity. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.
Moreover, when preparing using a roll mill, it can carry out by processing, for example, using a 3 roll mill, a 2 roll mill, etc., preferably cooling a pigment liquid mixture with cooling water etc.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is usually about 10 ⁸ dyn / sec. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

-(C) polyfunctional monomer-
The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,

A compound represented by the following formula (24):

Compound represented by the following formula (25)

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that ground stains, film residues and the like are hardly generated on the top.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.
The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (A) alkali-soluble polymers, Preferably it is 20-300 weight part. In this case, when the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, when it exceeds 500 parts by weight, for example, alkali developability is reduced. There is a tendency that background stains, film residues, etc. are likely to occur on the unexposed substrate or on the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include (a) an unsaturated carboxylic acid compound, (b) a hydroxyl group-containing unsaturated compound and (c) other polymerizable unsaturated compounds exemplified for the copolymer [α]. In addition to compounds similar to the compounds, N- (meth) acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products such as M-5600 (trade name, manufactured by Toagosei Co., Ltd.), etc. Can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting colored layer may be insufficient.
The total amount of the polyfunctional monomer and monofunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts per 100 parts by weight of the (A) alkali-soluble polymer. Parts by weight. In this case, if the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to decrease. There is a tendency that soiling, film residue, etc. are likely to occur on the substrate or the light shielding layer.

-(D) Photoradical generator-
The photo-radical generator in the present invention comprises the (C) polyfunctional monomer and optionally used monofunctional monomer by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. It is a compound capable of generating a radical capable of initiating polymerization.
Examples of such photo radical generators include biimidazole compounds, acetophenone compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, and triazine compounds. Compounds, carbazole compounds, and the like.
In the present invention, the photoradical generator can be used alone or in admixture of two or more. As the photoradical generator in the present invention, biimidazole compounds, acetophenone compounds, triazine compounds and At least one selected from the group of carbazole compounds is preferred.

Examples of the biimidazole compound include:
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-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,
Examples include 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, in particular 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole. Imidazole is preferred.
The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, has high sensitivity, sufficiently advances the curing reaction by exposure with a small amount of energy, and has a contrast. It is high and does not cause a curing reaction in the unexposed area. Therefore, the coated film after exposure is clearly divided into a cured part that is insoluble in the developer and an uncured part that has high solubility in the developer. Thus, it is possible to form a high-definition pattern array in which pixel patterns and black matrix patterns without undercuts are arranged according to a predetermined arrangement.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as the photoradical generator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As such a hydrogen donor, a mercaptan compound defined below, an amine compound defined below, and the like are preferable.
The mercaptan compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “mercaptan”). It is called "system hydrogen donor".
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound” "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

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

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

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In the amine-based hydrogen donor, at least one of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted group may be substituted at a position other than the amino group. Alternatively, it may be substituted with an unsubstituted phenoxycarbonyl group, nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples include ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable. In addition, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone can act as a photoradical initiator alone even in the absence of a biimidazole compound. .

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

Examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl And phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. That.
Among these acetophenone compounds, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and the like are preferable.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.
Examples of the benzophenone compounds include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone.
Examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone, and the like.
Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan -2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

A compound represented by the following formula (26):

等のハロメチル基を有する化合物等を挙げることができる。 Compound represented by the following formula (27)

And compounds having a halomethyl group.

  Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine and the like are particularly preferable.

  Examples of the carbazole-based compound include a compound represented by the following formula (28), a compound represented by (29), and the like.

[In the formula (28), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, carbon number 1 -20 alkyl group, cycloalkyl group having 3 to 8 carbon atoms, phenyl group which may be substituted, or monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). R ⁸ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ⁸ may be the same as or different from each other, and R ⁹ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or 4 to 4 carbon atoms. a monovalent sulfur-containing heterocyclic groups 20, R ⁹ where there are a plurality of phases May be the same as or different, a is an integer of 0-5, b is an integer of 0 to 5, which is (a + b) ≦ 5. ]

[In the formula (29), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, carbon number 1 -20 alkyl group, cycloalkyl group having 3 to 8 carbon atoms, phenyl group which may be substituted, or monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). R ⁸ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ⁸ may be the same as or different from each other, and R ⁹ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or 4 to 4 carbon atoms. a monovalent sulfur-containing heterocyclic groups 20, R ⁹ where there are a plurality of phases May be the same or different to, c is an integer of 0 to 5, d is an integer from 1 to 5, a (c + d) ≦ 5, e is an integer of 0 to 6. ]

In formula (28) and formula (29), examples of the alkyl group having 1 to 20 carbon atoms of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec- Examples include butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. be able to.
Further, the cycloalkyl group having a carbon number of R ⁵ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group.
In Formula (28) and Formula (29), R ⁵ is preferably, for example, a methyl group, an ethyl group, or the like.

In formula (28) and formula (29), examples of the alkyl group having 1 to 20 carbon atoms of R ⁶ and R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Etc. can be mentioned.
Moreover, as a C3-C8 cycloalkyl group of R < ⁶ > and R < ⁷ >, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned, for example.

Examples of the substituent for the phenyl group of R ⁶ and R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pentyl group. Group, an alkyl group having 1 to 6 carbon atoms such as n-hexyl group; a cycloalkyl group having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group: methoxy group, ethoxy group, n-propoxy group, i-propoxy group, an alkoxyl group having 1 to 6 carbon atoms such as an n-butoxy group and a t-butoxy group; a cycloalkyloxy group having 3 to 6 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group: a phenyl group; a fluorine atom, a chlorine atom, etc. A halogen atom etc. can be mentioned.

Examples of the monovalent alicyclic group having 7 to 20 carbon atoms of R ⁶ and R ⁷ (excluding the cycloalkyl group) include, for example, a group having a 1-alkylcycloalkane skeleton and a bicycloalkane skeleton. A group having a tricycloalkane skeleton, a group having a spiroalkane skeleton, a group having a terpene skeleton, a group having an adamantane skeleton, and the like.
In formula (28) and formula (29), R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group, an ethyl group, or the like.

In formula (28) and formula (29), examples of the alkyl group having 1 to 12 carbon atoms of R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec- Examples include butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. be able to.
Further, the cycloalkyl group having 3 to 8 carbon atoms R ^8, examples thereof include a cyclopentyl group, a cyclohexyl group.
As the alkoxyl group having 1 to 12 carbon atoms R ^8, for example, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, t-butoxy group, n- pentyloxy group, Examples thereof include an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, and an n-dodecyloxy group.
As the cycloalkyloxy group having 3 to 8 carbon atoms R ^8, for example, can be exemplified cyclopentyloxy, cyclohexyloxy group and the like.
In Formula (28) and Formula (29), R ⁸ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, an ethoxy group, or the like.

In formula (28) and formula (29), R ^{9 is} a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms and a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms. Examples of the group or monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms include thiolanyl group, azepinyl group, dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, Xidodanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, Pyrazinyl group, pyrrolinyl group, morphonyl group, piperazinyl group, quinuclidinyl group, indolyl group, Soydolyl group, benzofuranyl group, benzothiophenyl group, indolizinyl group, chromenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, Examples thereof include a thioxanthenyl group, a phenazinyl group, a phenothiazinyl group, a phenoxathinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.
In formula (28) and formula (29), R ⁹ is preferably a tetrahydrofuranyl group, a tetrahydropyranyl group, or the like.

In the formula (28), a is preferably 0, 1 or 2, particularly preferably 1, and b is preferably 0 or 1, particularly preferably 0.
In the formula (29), c is preferably 0, 1 or 2, particularly preferably 1, d is preferably 1, e is preferably 0, 1 or 2, and particularly preferably 1.

Specific examples of carbazole compounds include
1- [9-Ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate,

1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate,

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime)
Etc.

  Among these carbazole compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like are preferable, and in particular, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazole-3-i]]-1- (O-acetyloxime) and the like are preferable.

The amount of the photoradical generator used in the present invention is usually 0.01 to 200 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer optionally used. Part by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the total use amount of the photo radical generator is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a pattern array in which pixel patterns or black matrix patterns are arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 200 parts by weight, the formed colored layer tends to fall off from the substrate during development, and background stains, film residue, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer. Become.
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinking / sensitizer can be used in combination with the photoradical generator as necessary.

-Additives-
The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components, but may contain other additives as necessary.
As the additive, an organic acid or an organic amino compound (provided, for example, has an effect of further improving the dissolution characteristics of the radiation-sensitive composition in an alkaline developer and further suppressing the remaining undissolved product after development) The hydrogen donor is excluded).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the phenyl group via a carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, prevention of soiling and film residue on the substrate or the light-shielding layer in the unexposed area, and the like. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when the usage-amount of organic acid exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as ethylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri- n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine and tricyclohexylamine;
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino- Mono (cyclo) alkanolamines such as 1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclo Di (cyclo) alkanolamines such as hexanol) amine;
Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 -Tri (cyclo) alkanolamines such as cyclohexanol) amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1, 2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, for example,
Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in a solvent described later, prevention of background contamination and film residue on the unexposed portion of the substrate or the light shielding layer, and the like. And amino (cyclo) alkanediols are preferred, in particular, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention comprises the components (A) to (D) as essential components, and contains the additive components as necessary. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

As such a solvent, for example,
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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

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

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl acetoacetate, acetoacetate Le, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl Ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propylene Sulfonate, acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high-boiling solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.
The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the liquid composition is usually from 5 to 5 from the viewpoint of applicability and stability of the obtained liquid composition. The amount is 50% by weight, preferably 10 to 40% by weight.

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

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

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

  The color filter of the present invention thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like.

Liquid crystal display element The liquid crystal display element of this invention comprises the color filter of this invention.
Moreover, as one embodiment of the liquid crystal display element of the present invention, a pixel and / or a black matrix is formed on a thin film transistor substrate array as described above using the radiation-sensitive composition for forming a colored layer of the present invention. By forming, a liquid crystal display element having particularly excellent characteristics can be manufactured.

The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components. Specific examples of particularly preferred compositions are as follows. (G)
(A) (A) The alkali-soluble polymer contains (meth) acrylic acid as an essential component (a) an unsaturated carboxylic acid compound, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 1,2 (B) a hydroxyl group-containing unsaturated compound having at least one selected from the group consisting of dihydroxyethyl and 2,3-dihydroxypropyl (meth) acrylate as an essential component, styrene, methyl (meth) acrylate, n-propyl ( (C) at least one selected from the group of (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate and N-phenylmaleimide Obtained by reacting the silane compound (1) with a copolymer [α] with another unsaturated compound. Colored layer forming radiation-sensitive composition is a polymer.
(B) The radiation-sensitive composition for forming a colored layer according to (a) above, wherein the silane compound (1) comprises 3-methacryloyloxypropyltrimethoxysilane and / or 3-methacryloyloxypropyltriethoxysilane.
(C) The radiation-sensitive composition for forming a colored layer according to (a) or (b), which is produced through a process in which the copolymer [α] undergoes living radical polymerization.
(D) (C) The colored layer of (i) to (c) above, wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Radiation sensitive composition for forming.

(E) (D) The colored layer formation of (i) to (d) above, wherein the photoradical generator is at least one selected from the group consisting of biimidazole compounds, acetophenone compounds, triazine compounds and carbazole compounds. Radiation sensitive composition.
(F) The biimidazole compound is 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 It consists of at least one selected from the group of 5′-tetraphenyl-1,2′-biimidazole, and the acetophenone compound is 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one , 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one Small It is composed of at least one kind, the triazine compound is 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, and the carbazole compound is 1- [ 9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) The radiation-sensitive composition for forming a colored layer according to (e), comprising at least one selected from the group of (O).
(G) The radiation-sensitive composition for forming a colored layer according to (a) to (f) above, wherein the colorant contains an organic pigment and / or carbon black.

Further, the preferred color filter of the present invention is
(H) It has a pixel and / or a black matrix formed using the radiation-sensitive composition for forming a colored layer described in (a) to (g).

The preferred liquid crystal display element of the present invention is
(L) The color filter of (H) is provided,
A more preferred liquid crystal display element of the present invention is
(N) A pixel and / or black matrix formed using the radiation-sensitive composition for forming a colored layer described in (a) to (g) above is provided on a thin film transistor substrate array.

The (A) alkali-soluble polymer of the present invention has a reactive unsaturated group in the polymer side chain, and can be used particularly suitably as a component of a radiation-sensitive composition for forming a colored layer. In addition, it is also useful as a component of radiation-sensitive materials such as protective film formation for liquid crystal display elements, interlayer insulation film formation, spacer formation for liquid crystal display elements, microlens formation, paints, and adhesives. is there.
In addition, the radiation-sensitive composition for forming a colored layer of the present invention is highly sensitive and has excellent pattern shape, residual film ratio, etc., even when it contains a low amount of exposure and a high concentration of pigment, and it is a substrate. It is possible to form a pixel pattern and a black matrix pattern that are also excellent in adhesion to the substrate. Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters including color filters for liquid crystal display elements in the electronic industry.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Here, parts and% are based on weight.
Mw and Mn of the resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (manufactured by Showa Denko KK).
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.
Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 25 parts by weight of N-phenylmaleimide. , 10 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, 15 parts by weight of 2-hydroxyethyl methacrylate and 5 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent were added, and after nitrogen substitution, the mixture was gently stirred. While raising the temperature of the reaction solution to 80 ° C., polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobisisobutyronitrile was added, and polymerization was continued for another hour, whereby the copolymer [α] A solution (solid content concentration = 33.0 wt%) was obtained. The obtained copolymer [α] had Mw = 11,000 and (Mw / Mn) = 1.65. This copolymer [α] is referred to as “copolymer (α-1)”.
Next, 10 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (trade name Silaace S710, manufactured by Chisso Corporation) is added to the copolymer (α-1) solution, and the mixture is stirred at 60 ° C. for 3 hours. By making it react, the solution (solid content concentration = 35.0 weight%) of (A) alkali-soluble polymer was obtained. This (A) alkali-soluble polymer is referred to as “polymer (A-1)”.

Synthesis Examples 2-3
In Synthesis Example 1, each solution (A) of the alkali-soluble polymer (solid content) was the same as Synthesis Example 1 except that the addition amount of 3-methacryloyloxypropyltrimethoxysilane was changed to 5 parts by weight or 3 parts by weight. Concentration = 35.0% by weight). The obtained (A) alkali-soluble polymer is referred to as “polymer (A-2)” and “polymer (A-3)”, respectively.

Preparation of pigment dispersion Preparation Example 1
(B) C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 = 80/20 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of BYK-2001 (in terms of solid content) as a dispersant, and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent were processed by a bead mill. A pigment dispersion (R) was prepared.

Preparation Example 2
(B) C.I. I. Pigment green 36 / C.I. I. 20 parts by weight of Pigment Yellow 150 = 50/50 (weight ratio) mixture, 5 parts by weight of Solsperse 24000 as a dispersant, 0.5 part by weight of Solsperse 12000, and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (G) was prepared by treating with a bead mill.

Preparation Example 3
(B) 12 parts by weight of CI Pigment Blue 15: 6 / CI Pigment Violet 23 = 90/10 (weight ratio) as a colorant, 5 parts by weight of Solsperse 24000, 0.5 part by weight of Solsperse 5000 as a dispersant A pigment dispersion (B) was prepared by treating 0.5 parts by weight of 12000 and 62 parts by weight of propylene glycol monomethyl ether acetate and 20 parts by weight of cyclohexanone as a solvent using a bead mill.

Example 1
Pigment dispersion (R) 100 parts by weight, (A) 8.5 parts by weight of polymer (A-1) as alkali-soluble polymer, (C) 6.3 parts by weight of dipentaerythritol pentaacrylate as polyfunctional monomer Part and 6.3 parts by weight of dipentaerythritol hexaacrylate, (D) 4 parts by weight of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one as a photoradical generator and diethylthioxanthone 1 .5 parts by weight, perfluoroalkyl group-containing oligomer (trade name: Mega-Fac R08-MH, manufactured by Dainippon Ink Co., Ltd.) 0.3 part by weight and 3-methacryloxypropyltrimethoxysilane (trade name: Sila Ace S710) 0.4 parts by weight, manufactured by Chisso Corporation), and 30 parts by weight of cyclohexanone and propylene glycol monomer as a solvent. A liquid composition (R-1) was prepared by mixing 20 parts by weight of tilether acetate.

The liquid composition (R-1) was evaluated by forming a pattern according to the following procedure. The evaluation results are shown in Table 1.
Pattern formation The liquid composition (R-1) was applied on the surface of a glass substrate using a spin coater and then pre-baked at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. . Thereafter, the six substrates were cooled to room temperature, and a high pressure mercury lamp was used for the coating film on each substrate, and the coating film on each substrate was 300 J / m ² , 400 J / m ² , 500 J through a photomask. / M ² , 750 J / m ² , 1,000 J / m ^2, or 2,000 J / m ² . Thereafter, a 0.04 wt% aqueous potassium hydroxide solution at 23 ° C. was discharged onto the coating film on each substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development, and then 220 ° C. Was post-baked for 30 minutes to form a dot pattern of 200 × 200 μm.

Evaluation of sensitivity The dot pattern on each substrate is observed with a scanning electron microscope, the pattern is formed well, and the remaining film ratio calculated as the film thickness ratio before and after development (film thickness after development × 100 / development) When the previous film thickness is 90% or more, the pattern is formed well, but the remaining film ratio before and after development is less than 90%, or a part of the pattern is missing Was evaluated as Δ, and the case where no pattern was formed was evaluated as ×.

Evaluation of adhesion The liquid composition (R-1) was applied on the surface of a glass substrate using a spin coater and then pre-baked at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. did. Then, after cooling this board | substrate to room temperature, the coating film was exposed by the exposure amount of 2000 J / m < ² > using the high pressure mercury lamp. Thereafter, a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. was discharged at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development, and then post-baked at 220 ° C. for 30 minutes. Went. Then, according to the JIS K5400 standard, the coating film is cross-cut into 100 grids, and the adhesion is evaluated. If the grids do not peel off, 1 or 10 of the grids The case where peeling occurred was evaluated as Δ, and the case where more than 10 grids were peeled off was evaluated as ×.

Examples 2-3 and Comparative Example 1
Example 1 is the same as Example 1 except that the polymer (A-2), the polymer (A-3) or the copolymer (α-1) is used instead of the polymer (A-1). Thus, a liquid composition (R-2), a liquid composition (R-3) or a liquid composition (r-1) was prepared.
Subsequently, Example 1 was used except that the liquid composition (R-2), the liquid composition (R-3) or the liquid composition (r-1) was used in place of the liquid composition (R-1). Evaluation was performed in the same manner. The evaluation results are shown in Table 1.

Example 4
A liquid composition (G-1) was prepared in the same manner as in Example 1, except that the pigment dispersion (R) was changed to the pigment dispersion (G) in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid composition (G-1) was used instead of the liquid composition (R-1). The evaluation results are shown in Table 1.

Examples 5 to 6 and Comparative Example 2
Example 4 is the same as Example 4 except that the polymer (A-2), polymer (A-3) or copolymer (α-1) is used instead of the polymer (A-1). Then, a liquid composition (G-2), a liquid composition (G-3) or a liquid composition (g-1) was prepared.
Subsequently, Example 1 was used except that instead of the liquid composition (R-1), the liquid composition (G-2), the liquid composition (G-3) or the liquid composition (g-1) was used. Evaluation was performed in the same manner. The evaluation results are shown in Table 1.

Example 7
A liquid composition (B-1) was prepared in the same manner as in Example 1 except that the pigment dispersion (R) was changed to the pigment dispersion (B) in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid composition (B-1) was used instead of the liquid composition (B-1). The evaluation results are shown in Table 1.

Examples 8 to 9 and Comparative Example 3
Example 7 is the same as Example 7 except that the polymer (A-2), the polymer (A-3) or the copolymer (α-1) is used instead of the polymer (A-1). Thus, a liquid composition (B-2), a liquid composition (B-3) or a liquid composition (b-1) was prepared, respectively.
Subsequently, Example 1 was used except that the liquid composition (B-2), the liquid composition (B-3) or the liquid composition (b-1) was used in place of the liquid composition (R-1). Evaluation was performed in the same manner. The evaluation results are shown in Table 1.

Claims (5)

  The polymer main chain is composed of a monomer having a polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated carboxylic acid anhydride as an essential component, and a (meth) acryloyloxyalkylsilyl group and / or vinylsilyl is present in the polymer side chain. An alkali-soluble polymer having a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000 as measured by gel permeation chromatography (GPC), which has a group. (A) a polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated carboxylic acid anhydride, (b) a polymerizable unsaturated compound having one or more hydroxyl groups in one molecule, and (c) another polymerizable property. The alkali-soluble polymer of Claim 1 obtained by making the alkoxysilane compound represented by following formula (1) react with the copolymer with an unsaturated compound.

[In the formula (1), X represents a single bond or —OC (═O) — (where the oxygen atom on the left is bonded to Y), and Y represents a single bond when X is a single bond. When X is —OC (═O) —, it represents a methylene group or an optionally substituted alkylene group having 2 to 11 carbon atoms, and each R ¹ is independently a methyl group or a substituted group. And R ² represents a hydrogen atom or a methyl group. However, when both X and Y are single bonds, R ² represents a hydrogen atom. ]   (A) Coloring comprising the alkali-soluble polymer according to claim 1 or 2, (B) a colorant, (C) a polyfunctional monomer, and (D) a photoradical generator. A radiation-sensitive composition for layer formation.   A color filter having a colored layer formed using the radiation-sensitive composition for forming a colored layer according to claim 3.   A liquid crystal display device comprising the color filter according to claim 4.