JP5056025B2 - Radiation sensitive resin composition and color filter - Google Patents

Abstract

A radiation sensitive resin composition for a color filter, a color filter formed by using the composition, and a color LCD device containing the color filter are provided to improve voltage holding ratio and the solvent re-solubility of a dry coating and to prevent the generation of stain on a film after exposure and development. A radiation sensitive resin composition for a color filter comprises a colorant; an alkali-soluble resin; a multifunctional monomer; and a photopolymerization initiator, wherein the alkali-soluble resin is a copolymer of (b1) at least one selected from an unsaturated carboxylic acid, an unsaturated carboxylic anhydride and an unsaturated phenol compound, (b2) a compound containing an allyl group, and (b3) at least one unsaturated compound which is different from (b1) and (b2) and is selected from the group consisting of an aromatic vinyl compound, an indene, an N-substituted maleimide, a macromonomer having a (meth)acryloyl group at the one terminal of a polymer molecular chain, an unsaturated carboxylate, an unsaturated carboxylic acid aminoalkyl ester, an unsaturated carboxylic glycidyl ester, a vinyl carboxylate, an unsaturated ether, an unsaturated amide and an aliphatic conjugated diene. The alkali-soluble resin has a ratio (Mw/Mn) of a polystyrene-reduced weight average molecular weight(Mw) and a polystyrene-reduced number average molecular weight(Mn) by GPC is 1.0-2.0.

Description

  The present invention is formed from a radiation-sensitive resin composition useful for the production of a color filter used in a transmissive or reflective color liquid crystal device, a color imaging tube element, and the like, a method for preparing the same, and the radiation-sensitive resin composition. The present invention relates to a color filter and a color liquid crystal display device including the color filter.

As a method of forming a color filter using a colored radiation-sensitive resin composition, a coating film of a colored radiation-sensitive linear resin composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. Then, irradiation with radiation through a photomask having a desired pattern shape (hereinafter referred to as “exposure”) is performed with, for example, an alkali developer to dissolve and remove unexposed portions, and then using a clean oven or a hot plate A method of obtaining pixels of each color by post-baking (see, for example, Patent Document 1) is known.
In recent years, since the size of the substrate used for forming the color filter has increased, the colored radiation-sensitive resin composition coating method has been changed from a method using a central dropping type spin coater to the colored radiation-sensitive resin composition. The liquid outlet portion for application is being replaced by a method using a slit nozzle having a smaller diameter. In the latter slit nozzle method, since the diameter of the liquid outlet is small (narrow), the colored radiation-sensitive resin composition often remains around the tip of the nozzle after application, and when it is dried, the next application Since it sometimes drops onto the color filter as a dry foreign matter, and the quality of the color filter is significantly reduced, jet cleaning is usually carried out by spraying a cleaning solvent on the nozzle tip before coating, but it is still a color filter due to dry foreign matter. Therefore, it is not possible to effectively prevent the quality of the product from being deteriorated, which is a major factor in reducing the product yield. Furthermore, the conventional colored radiation-sensitive resin composition may cause uneven color in the film after exposure / development, which also causes a decrease in product yield.
Therefore, in recent years, in order to cope with such problems, the coloration for color filters, which is highly washable with a washing solvent, that is, highly soluble in the washing solvent even after drying and does not cause color unevenness in the film after exposure and development. There is a need for radiation sensitive resin compositions.

  Also, in recent years, in the technical field of color filters, there is a strong demand for color liquid crystal display devices that do not cause defects such as image sticking and afterimages over a long period of time with respect to display performance. There is an increasing demand for improvement in reliability related to electrical characteristics such as retention rate, but it is actually difficult to meet the demand with conventional colored radiation-sensitive resin compositions.

JP 2000-329929 A

  The problem of the present invention is that the solvent re-dissolvability of the dried coating film is excellent, the coating film after exposure / development does not cause color unevenness, and is excellent in terms of electrical characteristics such as voltage holding ratio. Another object of the present invention is to provide a radiation-sensitive resin composition or the like that can form a color filter with a high product yield.

The present invention, first,
A radiation-sensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (B) the alkali-soluble resin is (B1) one type selected from the group of unsaturated carboxylic acids or acid anhydrides and unsaturated phenol compounds, and (b2) a compound having an allyl group and another polymerizable unsaturated bond as a polymerizable unsaturated bond ; (B3) A copolymer with an unsaturated compound other than the above, and a polystyrene-converted weight average molecular weight (Mw) (hereinafter simply referred to as “Mw”) and gel measured by gel permeation chromatography (GPC). Ratio (Mw / Mn) to polystyrene-reduced number average molecular weight (Mn) (hereinafter simply referred to as “Mn”) measured by permeation chromatography (GPC) is 1.0 to 2. The radiation sensitive resin composition (hereinafter referred to as “radiation sensitive resin composition (I)”), which is 0, and (D) the photopolymerization initiator contains a carbazole-based compound as an essential component. Become.

The present invention secondly,
(A) The colorant is a pigment, and a pigment dispersion obtained by mixing and dispersing the pigment in a solvent in the presence of a dispersant is mixed (B) alkali-soluble resin, (C) polyfunctional And (D) a method for preparing a radiation-sensitive resin composition (I), which is mixed with a photopolymerization initiator.

Third, the present invention
It consists of the radiation sensitive resin composition (I) for color filters.

The present invention fourthly,
It consists of a color filter formed using the radiation sensitive resin composition (I).

The present invention fifthly,
A color liquid crystal display device including the color filter;

Hereinafter, the present invention will be described in detail.
Radiation sensitive resin composition (I)
-(A) Colorant-
The colorant in the radiation-sensitive resin composition (I) is not particularly limited, and may be any of a pigment, a dye, or a natural pigment, but the color filter has high purity and high light transmission color and heat resistance. Since it is required, a pigment is preferable, and an organic pigment or carbon black is particularly preferable.
Examples of the organic pigment include compounds classified as pigments in the color index, and specifically those having the following color index (CI) numbers.

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

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

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

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 Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60, CI Pigment Blue 80;
CI Pigment Green 7, CI Pigment Green 36;
CI Pigment Brown 23, CI Pigment Brown 25;
CI Pigment Black 1, CI Pigment Black 7.

Among these organic pigments, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment red 177, C.I. I. CI Pigment Red 254, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Green 7, CI Pigment Green 36; CI Pigment Violet 23, CI Pigment Blue 60 and CI Pigment Blue 80 At least one selected from the group is preferred.
The organic pigments can be used alone or in admixture of two or more, and organic pigments and carbon black can also be mixed and used.

  In the present invention, the radiation-sensitive resin composition (I) 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, which is to be described later as component (B), component (C) and component (D), and additional solvents as required It is preferable to prepare by adding other additives to be mixed.

As the dispersant used for the preparation of the pigment dispersion, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, but a compound having a urethane bond (hereinafter, “ Dispersants containing “urethane-based dispersants”) are preferred.
The urethane bond generally has the formula R′—NH—COO—R ″, where R ′ and R ″ are independently of each other an aliphatic, alicyclic or aromatic monovalent or polyvalent organic group. And the polyvalent organic group is further bonded to another group having a urethane bond or another group, and is present in a lipophilic group and / or a hydrophilic group in the urethane-based dispersant. And can be present in the main chain and / or side chain of the urethane-based dispersant, and can further be present in the urethane-based dispersant. When two or more urethane bonds are present in the urethane-based dispersant, each urethane bond may be the same or different.

Examples of such urethane dispersants include reaction products of diisocyanates and / or triisocyanates with polyesters having a hydroxyl group at one end and / or polyesters having a hydroxyl group at both ends. be able to.
Examples of the diisocyanates include benzene diisocyanates such as benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; toluene-2,4-diisocyanate, toluene-2 , 5-diisocyanate, toluene-2,6-diisocyanate, toluene diisocyanates such as toluene-3,5-diisocyanate; 1,2-xylene-3,5-diisocyanate, 1, 2-xylene-3,6-diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-4,6- Other aromatics such as xylene diisocyanates such as diisocyanate, 1,4-xylene-2,5-diisocyanate, 1,4-xylene-2,6-diisocyanate Mention may be made of an isocyanate, and the like.

Examples of the triisocyanates include benzene such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, and benzene-1,3,5-triisocyanate. Triisocyanates; toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-tri Toluene isocyanates such as isocyanate; 1,2-xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2, 4,5-triisocyanate, 1,3-xylene-2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4-chi Other aromatic triisocyanates such as xylene triisocyanates such as len-2,3,5-triisocyanate and 1,4-xylene-2,3,6-triisocyanate can be mentioned. .
These diisocyanates and triisocyanates can be used alone or in admixture of two or more.

Examples of the polyester having a hydroxyl group at one end and the polyester having a hydroxyl group at both ends include polycaprolactone having a hydroxyl group at one end or both ends, polyvalerolactone having a hydroxyl group at one end or both ends, and one end Or polylactones having a hydroxyl group at one or both ends, such as polypropiolactone having a hydroxyl group at both ends; polyethylene terephthalate having a hydroxyl group at one or both ends, polybutylene terephthalate having a hydroxyl group at one or both ends, etc. Examples thereof include polycondensed polyesters having a hydroxyl group at one or both ends.
These polyesters having a hydroxyl group at one end and polyesters having a hydroxyl group at both ends can be used alone or in admixture of two or more.

The urethane-based dispersant in the present invention is preferably a reaction product of an aromatic diisocyanate and a polylactone having a hydroxyl group at one end and / or a polylactone having a hydroxyl group at both ends, particularly toluene diisocyanate. A reaction product of a polycaprolactone having a hydroxyl group at one end and / or a polycaprolactone having a hydroxyl group at both ends is preferred.
Specific examples of such urethane-based dispersants are trade names such as Disperbyk161 and Disperbyk170 (above, manufactured by BYK Chemy (BYK)), EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disparon (Enomoto) Series products such as Kasei Co., Ltd.) can be mentioned.
The Mw of the urethane-based dispersant in the present invention is usually 5,000 to 50,000, preferably 7,000 to 20,000.
The said urethane type dispersing agent can be used individually or in mixture of 2 or more types.

A (meth) acrylic dispersant composed of a (co) polymer of (meth) acrylic monomers is also preferred as the dispersant.
Specific examples of such (meth) acrylic dispersants include Disperbyk 2000 and Disperbyk 2001 (above, manufactured by BYK Corporation) as trade names.
The said (meth) acrylic-type dispersing agent can be used individually or in mixture of 2 or more types.

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. Preferably it is 10-50 weight part. 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 resin 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 1000 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 mixed solution 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.

-(B) Alkali-soluble resin-
The alkali-soluble resin in the radiation-sensitive resin composition (I) is (b1) one type selected from the group of unsaturated carboxylic acids or acid anhydrides and unsaturated phenol compounds (hereinafter referred to as “unsaturated compound (b1)”). And (b2) a compound having an allyl group and another polymerizable unsaturated bond as the polymerizable unsaturated bond (hereinafter referred to as “unsaturated compound (b2)”), and (b3) other than the above It is a copolymer with an unsaturated compound (hereinafter referred to as “unsaturated compound (b3)”) (hereinafter, the components (b1) to (b3) are collectively referred to as “polymerizable unsaturated compound”), And it consists of a copolymer (henceforth "copolymer (B1)") whose ratio (Mw / Mn) of Mw and Mn is 1.0-2.0.

Among unsaturated compounds (b1), examples of unsaturated carboxylic acids or acid anhydrides thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; Unsaturated dicarboxylic acids such as acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; Substances: Mono [(meth) acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc. Esters; polymers having carboxy groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate And mono (meth) acrylates.
Of these unsaturated carboxylic acids or acid anhydrides thereof, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively light ester HOA-MS and light ester HOA-MPE ( As mentioned above, it is marketed under the trade name of Kyoeisha Chemical Co., Ltd.

  Examples of the unsaturated phenol compound include o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, unsaturated phenols such as m-isopropenylphenol and p-isopropenylphenol; 2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, Examples thereof include unsaturated naphthols such as 2-isopropenyl-1-naphthol and 3-isopropenyl-1-naphthol.

  In the present invention, the unsaturated compound (b1) includes (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylphenol, and the like. Are preferred, and (meth) acrylic acid is particularly preferred.

  Examples of the unsaturated compound (b2) include allyl (meth) acrylate, allyl crotonate, allyl α-chloroacrylate, allyl cinnamate, monoallyl maleate, monoallyl fumarate, and the like. Of these, allyl (meth) acrylate is particularly preferable.

  The unsaturated compound (b2) can be used alone or in admixture of two or more.

Moreover, as an unsaturated compound (b3), for example,
Styrene, α-methylstyrene, p-styrenesulfonic acid, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- Aromatic vinyl compounds such as vinyl benzyl methyl ether, m-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;

N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methyl N- (substituted) arylmaleimides such as phenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, and N-substituted maleimides such as N-cyclohexylmaleimide;
A macromonomer having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane or the like (hereinafter simply referred to as “macromonomer”). Kind;

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, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, propylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, isobornyl (meta ) Unsaturated carboxylic acids such as acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol (meth) acrylate, etc. Esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl ( Unsaturated carboxylic acid aminoalkyl esters such as (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Examples thereof include aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene and isoprenesulfonic acid.

Among these unsaturated compounds (b3), styrene, macromonomers, N-substituted maleimides, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate Glycerol mono (meth) acrylate and the like are preferable, and among the macromonomers, polystyrene macromonomer, polymethyl (meth) acrylate macromonomer and the like are particularly preferable. Among the N-substituted maleimides, N-phenylmaleimide, N-cyclohexylmaleimide and the like are particularly preferable.
The unsaturated compound (b3) can be used alone or in admixture of two or more.

  In the present invention, the preferred copolymer (B1) is more specifically (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth). An unsaturated compound (b1) comprising at least one selected from the group of acrylates, an unsaturated compound (b2) comprising allyl (meth) acrylate as an essential component, a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, N -At least one selected from the group of phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol mono (meth) acrylate as an essential component, and optionally styrene, methyl (meta ) Acrylate and fu Mentioning a copolymer (B1) (hereinafter referred to as “copolymer (B1-1)”) of a mixture with an unsaturated compound (b3) containing at least one selected from the group of nyl (meth) acrylates. Can

More specifically, the copolymer (B1) is more preferably an unsaturated compound (b1) containing (meth) acrylic acid as an essential component and optionally containing succinic acid mono [2- (meth) acryloyloxyethyl]. ), Unsaturated compound (b2) having allyl (meth) acrylate as an essential component, polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) An essential component is at least one selected from the group of acrylate, benzyl (meth) acrylate and glycerol mono (meth) acrylate, and at least one selected from the group of styrene, methyl (meth) acrylate and phenyl (meth) acrylate. An unsaturated compound (b3 Mixture copolymer (B1) (hereinafter, referred to as "copolymer (B1-2)".) Between the like.

As specific examples of the copolymer (B1-2),
(Meth) acrylic acid / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / polystyrene macromonomer / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / polymethyl (meth) acrylate macromonomer / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

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

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / N-phenylmaleimide / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer, etc. Can be mentioned.

As specific examples of the copolymer (B1-1) other than the copolymer (B1-2),
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / polystyrene macromonomer / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / polymethyl (meth) acrylate macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / polystyrene macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / polymethyl (meth) acrylate macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / styrene copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate Copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / styrene copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / styrene Copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene Copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / glycerol Examples thereof include a mono (meth) acrylate / styrene copolymer.

In the copolymer (B1), the copolymerization ratio of the unsaturated compound (b1) is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the unsaturated compound (b2) is The copolymerization ratio of the unsaturated compound (b3) is preferably 1 to 80% by weight, particularly preferably 5 to 60% by weight. .
In the present invention, by setting the copolymerization ratio of each unsaturated compound in the copolymer (B1) within the above range, the radiation-sensitive resin composition (I) excellent in sensitivity, substrate adhesion, solvent resistance and the like. Can be obtained.

Mw / Mn of the copolymer (B1) is 1.0 to 2.0, preferably 1.0 to 1.7, particularly preferably 1.0 to 1.4.
The Mw of the copolymer (B1) is preferably 1,000 to 45,000, more preferably 3,000 to 20,000, and particularly preferably 4,000 to 10,000.
By using such a copolymer (B1) having a predetermined Mw / Mn, and preferably having the specific Mw, a radiation sensitive resin composition (I) excellent in developability can be obtained. As a result, pixels having sharp pattern edges can be formed, and residues, background stains, film residues, etc. are hardly generated on the unexposed substrate and the light-shielding layer during development, and cleaning with an organic solvent is possible. Therefore, it is possible to achieve a high product yield without producing dry foreign matters during the production of the color filter, and to effectively prevent “burn-in” of the color filter.
In the radiation sensitive resin composition (I), the copolymer (B1) can be used alone or in admixture of two or more.

The copolymer (B1) can be produced, for example, by polymerizing a polymerizable unsaturated compound in a solvent in the presence of a radical polymerization initiator system that generates a living radical.
In living radical polymerization, if 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. Then, the functional group in the polymerizable unsaturated compound is polymerized while being protected by, for example, esterification, and then deprotected, whereby the copolymer (B1) 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. (See, for example, Non-Patent Document 1), the odor proposed by Matyjazewski 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 2, Patent Document 3 and Patent Document 4. 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, and the like, 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 2 to 4.

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 2 to 5, by conducting living radical polymerization of a polymerizable unsaturated compound in the presence of a thiocarbonylthio compound and a radical initiator, a random copolymer or block copolymer having a narrow molecular weight distribution is obtained. 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 6), photoresist ( It has been clarified that it can be used for applications such as Patent Document 7) and surfactant (see Patent Document 8).

  In the present invention, a preferable copolymer (B1) is a group represented by the following formula (i) (hereinafter referred to as “terminal group (i)”) at least one terminal of each polymer chain constituting the copolymer (B1). ) Or a group represented by the formula (ii) (hereinafter referred to as “terminal group (ii)”) (hereinafter referred to as “thiocarbonylthio-terminated copolymer (B1)”). Can do.

[In the 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 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 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 an extraneous 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 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 terminal copolymer (B1) has only one polymer chain, the terminal group (i) is usually bonded to one terminal of the polymer chain, while the other A terminal group (i), a terminal group (ii), or a chain terminating group can 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 ¹ in formula (1) described later or R ² in formula (2) 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 ¹ in formula (1) described later or R ² in formula (2) 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 Z ¹ in formula (1) described later can be exemplified.

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

  The thiocarbonylthio-terminated copolymer (B1) is, for example, a step of living radical polymerization of a polymerizable unsaturated compound using a thiocarbonylthio compound represented by the following formula (1) or formula (2) as a molecular weight control agent. In this living radical polymerization, a radical initiator is usually also used.

[In the formula (1), 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, a 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 ¹ 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, the number of carbon atoms An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and hetero atoms, p ≧ 2 In this case, 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, a total number of atoms of 3 to 20 carbon atoms and hetero atoms A p-valent group derived from the above heterocyclic compound or a p-valent group having a polymer chain, wherein the alkyl group having 1 to 20 carbon atoms and the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms , Monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent heterocyclic group having 3 to 20 atoms in total, R, alkane having 1 to 20 carbon atoms The derived p-valent group, the p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and the p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted. Good. ]

[In the formula (2), 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 ² may have 1 to 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 monovalent heterocyclic group, -OR, -SR, represent a monovalent group having a -N (R) ₂ or a polymer chain, each R is the phase 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 number of atoms of 3 to 18 carbon atoms and hetero atoms. Wherein the alkyl group has 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group has 3 to 20 carbon atoms, and the monovalent aromatic hydrocarbon has 6 to 20 carbon atoms. The group, the 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 formula (1), 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, a 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, and 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 (1), 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 the formula (1), a plurality of Z ¹ may be the same or different from each other.

In the formula (1), when p = 1, R ¹ 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, a monovalent heterocyclic group having 3 to 20 total 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 corresponding groups of Z ¹ can be given. In a monovalent group having a polymer chain of R ¹ (p = 1), even when the polymer chain is directly bonded to the sulfur atom in the formula (1), 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 (1).

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.

In addition, when p ≧ 2, R ¹ 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 that is different from the carbon atom. 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, an aromatic hydrocarbon The p-valent group and the p-valent group derived from the heterocyclic compound having a total of 3 to 20 atoms may each 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, the carbon atom of each methyl group at the 1,4-position is a sulfur atom in the formula (1)). ), 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 (1).) 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 (1)) 1,4-di-i-propylbenzene (for example, the carbon atom at the 2-position of each i-propyl group at the 1,4-position is bonded to the sulfur atom in the formula (1)). Examples include naphthalene and anthracene groups.

  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.

P-valent group derived from the alkane having 1 to 20 carbon atoms, p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total. Examples of the substituent for the above 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 number of 3 atoms of carbon atoms and hetero atoms. -20 monovalent heterocyclic groups and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are present in one or more or one or more kinds in the substituted derivative. be able to. 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 giving the p-valent group of R ¹ include addition polymerization polymer chains, polyaddition polymer chains and polycondensation systems exemplified for the monovalent group having the Z ¹ polymer chain. The thing similar to a polymer chain can be mentioned. In the p-valent group having the polymer chain of R ¹ , even when the polymer chain is directly bonded to the sulfur atom in the formula (1), 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 (1).

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

In the formula (2), R ² 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 ² , 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) may be through a linking hand CH ₂ CH ₂ -COO-, etc. attached to the sulfur atom in the formula (2).
In addition, examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ² and substituted derivatives thereof include, for example, monovalent fat having 3 to 20 carbon atoms of R ¹ (p = 1). The thing similar to the group illustrated about the cyclic hydrocarbon group and its substituted derivative can be mentioned.
In the formula (2), a plurality of R ² may be the same as or different from each other.
In Formula (2), when the connecting part between Z ² and —C (═S) —S—R ² is an aliphatic carbon atom, the aliphatic carbon atom in Z ² is —C (═S ) When bonded to —S—R ² and the linking moiety is an aromatic carbon atom, the aromatic carbon atom in Z ² is bonded to —C (═S) —S—R ^2, and When the moiety is a sulfur atom, the sulfur atom in —SR representing Z ² is bonded to —C (═S) —S—R ² .

  Specific examples of particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (3) to (22).

These thiocarbonylthio compounds can be used alone or in admixture of two or more.
In the present invention, in living radical polymerization, together with the thiocarbonylthio compound, one or more other molecular weight control agents such as α-methylstyrene dimer, t-dodecyl mercaptan and the like can be used in combination.

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, 2,2′-azobisisobutyrate. Azo compounds such as nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, 1 , 1'-bis (t-butylperoxy) cyclohexane, organic peroxides such as t-butylperoxypivalate; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents. it can.
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;
Ketoalcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one;

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.

Of these solvents, propylene glycol monomethyl ether and ethylene glycol monomethyl are used from the viewpoints of solubility of each component, pigment dispersibility, coatability and the like when the liquid composition of the radiation sensitive resin composition (I) described later is used. Ether acetate, 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, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropio Over preparative 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.

The copolymer (B1) can also be produced by radical polymerization of a polymerizable unsaturated compound and then purification through a reprecipitation method using two or more organic solvents having different polarities.
The radical polymerization for producing a copolymer to be subjected to purification (hereinafter referred to as “unpurified copolymer”) is not particularly limited, and can be carried out by a conventional method.
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 radical polymerization, the resulting unpurified copolymer is purified by a reprecipitation method using two or more organic solvents having different polarities. That is, after removing 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, out 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 (B1).

  Examples of the good solvent / precipitant combination used in this reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, methyl ethyl ketone / n-heptane, and the like. Can be mentioned.

  During reprecipitation of the unpurified copolymer, it is desirable to add the polymer solution as little as possible while vigorously worring the precipitant, thereby minimizing the amount of impurities incorporated into the precipitate. . Moreover, the purity of a copolymer (B1) can be made higher by repeating a reprecipitation process in multiple times. When the precipitated copolymer (B1) 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, which is a modification 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 (B1) 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 precipitant (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 (B1) having a narrow molecular weight range can be fractionated with a high yield. Each fraction of the copolymer (B1) 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 (B1) obtained by such a reprecipitation method can be further purified by adsorption / affinity chromatography, dialysis method, or the like, if necessary.

  The amount of the alkali-soluble resin used in the radiation sensitive resin composition (I) is usually 10 to 1,000 parts by weight, preferably 20 to 500 parts by weight with respect to 100 parts by weight of the colorant (A). In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability may be lowered, or background stains or film residues may be generated on the substrate or the light shielding layer in the unexposed area. When the amount exceeds 1,000 parts by weight, the pigment concentration is relatively lowered, and it may be difficult to achieve the target color concentration as a thin film.

-(C) polyfunctional monomer-
The polyfunctional monomer in the radiation sensitive resin composition (I) is a monomer having two or more polymerizable unsaturated bonds. As such a polyfunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol of diethylene glycol or higher, polypropylene glycol of dipropylene glycol or higher;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Polymer di (meth) acrylates having hydroxyl groups at both ends, such as poly-1,3-butadiene having hydroxyl groups at both ends, polyisoprene having hydroxyl groups at both ends, polycaprolactone having hydroxyl groups at both ends,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferable. Specifically, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and di Pentaerythritol hexaacrylate is preferred because it has high pixel strength, excellent pixel surface smoothness, and is less likely to cause scumming or film residue on the unexposed substrate and the light shielding layer. The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The amount of the polyfunctional monomer used in the radiation sensitive resin composition (I) is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the copolymer (B1). is there. 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 pixel tend to be reduced. On the other hand, when the amount exceeds 500 parts by weight, for example, alkali developability is reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the 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 the unsaturated compound (b1), unsaturated compound (b2) and unsaturated compound (b3) exemplified for the copolymer (B1), as well as N-vinylsuccinimide. N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N- N-vinyl nitrogen-containing complexes such as vinyl indole, N-vinyl indoline, N-vinyl benzimidazole, N-vinyl carbazole, N-vinyl piperidine, N-vinyl piperazine, N-vinyl morpholine, N-vinyl phenoxazine Cyclic compound; N- (meth) acryloylmorpholine or a commercial product under the trade name M-5 00, M-5400, M-5600 (manufactured by Toagosei Co., Ltd.), and the like can be given.
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 pixel tend to be lowered.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the radiation-sensitive resin composition (I) contains a carbazole compound as an essential component, and is exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. Is a compound that yields an active species capable of initiating polymerization of the functional monomer and optionally the monofunctional monomer used.
In the present invention, other photopolymerization initiators can be used in combination with the carbazole compound.
Examples of the other photopolymerization initiator include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds. Among these other photopolymerization initiators, at least one selected from the group of acetophenone compounds, biimidazole compounds, and triazine compounds is preferable .
In the present invention, the carbazole compounds can be used alone or in admixture of two or more, and the other photopolymerization initiators can be used alone or in admixture of two or more.

  In the radiation sensitive resin composition (I), the general use amount of the photopolymerization initiator is usually (C) based on 100 parts by weight of the total of the polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which a pixel pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 80 parts by weight, the formed pixels tend to fall off the substrate during development.

    Examples of the carbazole-based compound include a compound represented by the following formula (23) (hereinafter referred to as “carbazole-based compound (1)”) and a compound represented by the following formula (24) (hereinafter referred to as “carbazole-based compound”). Compound (2) ") and the like.

[In the formula (23), R ³ 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 ⁴ and R ⁵ 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 ⁶ 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 ⁶ may be the same as or different from each other, and R ⁷ 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 ⁷ 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 (24), R ³ 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 ⁴ and R ⁵ 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 ⁶ 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 ⁶ may be the same as or different from each other, and R ⁷ 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 ⁷ 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 (23) and Formula (24), examples of the alkyl group having 1 to 20 carbon atoms of R ³ 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 ^3, examples thereof include a cyclopentyl group, a cyclohexyl group.
In Formula (23) and Formula (24), R ³ is preferably, for example, a methyl group, an ethyl group, or the like.

In formula (23) and formula (24), examples of the alkyl group having 1 to 20 carbon atoms of R ⁴ and R ⁵ 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.
Moreover, as a C3-C8 cycloalkyl group of R < ⁴ > and R < ⁵ >, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned, for example.

Examples of the substituent for the phenyl group of R ⁴ and R ⁵ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl. 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 ⁴ and R ⁵ (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 (23) and formula (24), R ⁴ and R ⁵ are preferably a hydrogen atom, a methyl group, an ethyl group, or the like.

In Formula (23) and Formula (24), examples of the alkyl group having 1 to 12 carbon atoms of R ⁶ 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.
Moreover, as a C3-C8 cycloalkyl group of R < ⁶ >, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned, for example.

Moreover, as a C1-C12 alkoxyl group of R < ⁶ >, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, Examples include n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group and the like.
Moreover, as a C3-C8 cycloalkyloxy group of R < ⁶ >, a cyclopentyloxy group, a cyclohexyloxy group, etc. can be mentioned, for example.
In Formula (23) and Formula (24), R ⁶ 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 the formula (23) and (24), a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms R ^7, monovalent nitrogen-containing heterocyclic group, or 4 carbon having 4 to 20 carbon atoms Examples of the monovalent sulfur-containing heterocyclic group of 20 include, for example, a thiolanyl group, an azepinyl group, a dihydroazepinyl group, a dioxolanyl group, a triazinyl group, an oxathanyl group, a thiazolyl group, an oxadiazinyl group, a dioxaindanyl group, Anaphthalenyl 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, isoindolyl 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, thioxanthenyl group A phenazinyl group, a phenothiazinyl group, a phenoxathinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like.
In Formula (23) and Formula (24), R ⁷ is preferably a tetrahydrofuranyl group, a tetrahydropyranyl group, or the like.

  In the formula (23), a is preferably 0, 1 or 2, particularly preferably 1, and b is preferably 0 or 1, particularly preferably 0.

  In the formula (24), 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 the carbazole compound (1) 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-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)
Etc.

Specific examples of the carbazole compound (2) include
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) and the like.

Of these carbazole compounds (1) and carbazole compounds (2), 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, ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3). -Dioxolanyl) methoxybenzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.
The carbazole compounds can be used alone or in admixture of two or more.

In the radiation sensitive resin composition (I), the amount of the carbazole compound used is usually 0.01 with respect to the total of 100 parts by weight of the (C) polyfunctional monomer and the monofunctional monomer. -80 parts by weight, preferably 1-60 parts by weight, more preferably 1-30 parts by weight. In this case, if the amount of the carbazole compound used is less than 0.01 parts by weight, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which a pixel pattern is arranged according to a predetermined arrangement, If it exceeds 80 parts by weight, the formed pixels tend to fall off the substrate during development.

Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1, , 2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and the like.
Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone -1,1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and the like are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

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

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

These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. those never cured at an exposure portion occurs.
The biimidazole compounds can be used alone or in admixture of two or more.

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

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

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

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

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

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

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 pixels are difficult to drop off from the substrate during development, and that the pixel intensity and sensitivity are high.
Specific examples of the combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-bis. (Diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

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

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

-Other additives-
Although the radiation sensitive resin composition (I) has the components (A) to (D) as essential components, it may further contain other additives as necessary.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Examples thereof include an aggregation inhibitor such as sodium acrylate.

Preparation of liquid composition The radiation-sensitive resin composition (I) is usually prepared as a liquid composition by blending a solvent. As said solvent, (A)-(D) component which comprises radiation sensitive resin composition (I), and another additive component are disperse | distributed or melt | dissolved, and it does not react with these components, but moderate volatility As long as it has, it can be appropriately selected and used.

As such a solvent, for example,
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;
Ketoalcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one;

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, 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, 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, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-acetate 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.

Further, together 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 point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
The high boiling point 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 preferably 5 from the viewpoint of applicability and stability of the obtained liquid composition. An amount of -50% by weight, particularly preferably 10-40% by weight is desirable.

Method of forming a color filter Next, using the radiation-sensitive resin composition (I), a method for forming a color filter of the present invention.
The method for forming a color filter usually includes at least the following steps (1) to (4).
(1) The process of forming the coating film of radiation sensitive resin composition (I) on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) A step of developing the coated film after exposure.
(4) A step of heat-treating (hereinafter referred to as “post-bake”) the coated film after development.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, a light-shielding layer is formed on the surface of the substrate, if necessary, so as to divide the pixel forming portion, and the radiation-sensitive resin composition (I) containing, for example, a red pigment is formed on the substrate. After the liquid composition is applied, pre-baking is performed to evaporate the solvent to form a coating film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
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 the liquid composition to the substrate, an appropriate coating method such as spin coating (coating with a spin coater), casting coating, roll coating, or coating with a slit nozzle can be employed. The radiation resin composition (I) has high solubility in a cleaning solvent even after drying, and is suitable for application by a slit nozzle.
The prebaking condition is usually about 2 to 4 minutes at 70 to 110 ° C.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, and more preferably 0.2 to 6.0 μm as the film thickness after removal of the solvent.

-(2) Process-
Thereafter, at least a part of the formed coating film is exposed, for example, through a photomask having an appropriate pattern. As the radiation used in this step, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of radiation is usually, 10~10,000J / m ² approximately.

-(3) Process-
Thereafter, the exposed coating film is preferably developed using an alkali developer, and an unexposed portion of the coating film is dissolved and removed to form a pattern.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of 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 about 5 to 300 seconds at room temperature.

-(4) Process-
Thereafter, by post-baking the developed coating film, a substrate on which red pixel patterns made of a cured product of the radiation-sensitive resin composition (I) are arranged in a predetermined arrangement can be obtained. The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.5 to 3.0 μm.

Further, by repeating the steps (1) to (4) using each liquid composition of the radiation sensitive resin composition (I) containing a green or blue pigment, a green pixel pattern and a blue By forming the pixel pattern on the same substrate, a colored layer in which pixel patterns of the three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the order of forming the pixel patterns of the respective colors in the present invention is not limited to the order described above.
The black matrix can be formed in the same manner as in the case of the pixel using the radiation-sensitive resin composition (I) containing a black pigment.

Color filter The color filter of the present invention is formed using the radiation-sensitive resin composition (I) of the present invention.
The color filter of the present invention is extremely useful for, for example, a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor and the like.

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

The radiation-sensitive resin composition (I) of the present invention has excellent solvent re-solubility of the dried coating film, does not cause color unevenness in the film after exposure and development, and has electrical characteristics represented by voltage holding ratio and the like. Therefore, it is possible to form a color filter having excellent reliability in terms of high product yield.
Therefore, the radiation-sensitive resin composition (I) of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display devices 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.
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 (trade name, 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
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, 200 parts by weight of dipropylene glycol dimethyl ether Subsequently, 20 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenylmaleimide, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, and 10 parts by weight of 2-methacryloyloxyethyl succinate were charged with nitrogen. Thereafter, the reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and polymerization was continued for another 2 hours, whereby a solution of the copolymer (B1) (S— 1) (solid content concentration = 33.0 wt%) was obtained. This copolymer (B1) had Mw = 6,000 and Mw / Mn = 1.4. This copolymer (B1) is referred to as “copolymer (S-1)”.

Synthesis example 2
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, 200 parts by weight of dipropylene glycol dimethyl ether Methacrylic acid 20 parts by weight, N-phenylmaleimide 18.8 parts by weight, allyl methacrylate 20 parts by weight, styrene 11.2 parts by weight, succinic acid 2-methacryloyloxyethyl 10 parts by weight, 2-hydroxyethyl methacrylate 10 After charging a part by weight and substituting with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and polymerization was continued for another 2 hours, whereby a solution of the copolymer (B1) (S— 2) (solid content concentration = 33.0 wt%) was obtained. This copolymer (B1) had Mw = 6,500 and Mw / Mn = 1.5. This copolymer (B1) is referred to as “copolymer (S-2)”.

Synthesis example 3
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, 200 parts by weight of dipropylene glycol dimethyl ether Subsequently, 20 parts by weight of methacrylic acid, 18.8 parts by weight of N-phenylmaleimide, 30 parts by weight of allyl methacrylate, 11.2 parts by weight of styrene, and 10 parts by weight of 2-methacryloyloxyethyl succinate were charged with nitrogen. Thereafter, the reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and polymerization was continued for another 2 hours, whereby a solution of the copolymer (B1) (S— 3) (solid content concentration = 33.0 wt%) was obtained. This copolymer (B1) had Mw = 6,000 and Mw / Mn = 1.4. This copolymer (B1) is referred to as “copolymer (S-3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 2 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 20 parts by weight of methacrylic acid and 31.2 parts by weight of N-phenylmaleimide. 1 part by weight, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 10 parts by weight of 2-methacryloyloxyethyl succinate, 4 parts by weight of α-methylstyrene dimer (molecular weight control agent) While stirring, the temperature of the reaction solution was raised to 80 ° C., and this temperature was maintained for polymerization for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for another 1 hour to obtain a copolymer solution (S-4). (Solid concentration = 33.0 wt%) was obtained. This copolymer had Mw = 46,000 and Mw / Mn = 4.7. This copolymer is referred to as “copolymer (S-4)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 12 parts by weight of 2,2′-azobisisovaleronitrile and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 20 parts by weight of methacrylic acid and 31.2 parts by weight of N-phenylmaleimide. , 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 10 parts by weight of 2-methacryloyloxyethyl succinate, and 10 parts by weight of α-methylstyrene dimer (molecular weight control agent) were substituted with nitrogen, and then gently stirred. However, the temperature of the reaction solution was raised to 70 ° C., and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, while maintaining the reaction solution at 70 ° C., 3 parts by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for 2 hours to obtain a copolymer solution (S-5). (Solid concentration = 32.4% by weight) was obtained. This copolymer had Mw = 6,000 and Mw / Mn = 2.5. This copolymer is referred to as “copolymer (S-5)”.

Synthesis Example 6
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, 200 parts by weight of dipropylene glycol dimethyl ether Then, 20 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenylmaleimide, 30 parts by weight of benzyl methacrylate, and 18.8 parts by weight of styrene were added, and the reaction solution was stirred while gently stirring. The temperature was raised to 80 ° C., and the polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for another hour to obtain a copolymer solution (S-6). (Solid concentration = 33.0 wt%) was obtained. This copolymer had Mw = 6,000 and Mw / Mn = 1.4. This copolymer is referred to as “copolymer (S-6)”.

Evaluation of solvent resolubility
Reference example 1
(A) C.I. I. Pigment red 254 and C.I. I. A mixture of 40 parts by weight of a 50/50 (weight ratio) mixture with Pigment Yellow 139, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was added to Diamond Fine Mill (trade name, A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) the solution (S-1) as an alkali-soluble resin, the amount of 70 parts by weight of the copolymer (S-1), and (C) the polyfunctional monomer 80 parts by weight of dipentaerythritol hexaacrylate, (D) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator, and propylene glycol monomethyl ether as a solvent A liquid composition (r-1) was prepared by mixing 1,000 parts by weight of acetate.
Next, the liquid composition (r-1) is spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface. A coating film was formed by drying after standing for a period of time.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference example 2
The liquid composition (S-2) was replaced with the liquid composition (S-2) in the same manner as in Reference Example 1 except that the solution (S-2) was used in an amount of 70 parts by weight of the copolymer (S-2). r-2) was prepared and a coating film was formed on a soda glass substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference example 3
The liquid composition (S-3) was replaced with the liquid composition (S-3) in the same manner as in Reference Example 1, except that the copolymer (S-3) was used in an amount of 70 parts by weight. r-3) was prepared, and a coating film was formed on a soda glass substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Example 1
(A) C.I. I. Pigment red 254 and C.I. I. A mixture of 40 parts by weight of a 50/50 (weight ratio) mixture with Pigment Yellow 139, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was added to Diamond Fine Mill (trade name, A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) the solution (S-1) as an alkali-soluble resin, the amount of 70 parts by weight of the copolymer (S-1), and (C) the polyfunctional monomer 80 parts by weight of dipentaerythritol hexaacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl as a photopolymerization initiator } -9. H. -Carbazole-3-i] -1- (O-acetyloxime) 50 parts by weight and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (r-4) .
Next, the liquid composition (r-4) is spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface. A coating film was formed by drying after standing for a period of time .
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Comparative Example 1
Instead of the solution (S-1), the solution (S-4) was used in such an amount that the copolymer (S-4) was 70 parts by weight, and (D) the photopolymerization initiator was 2-benzyl-2-dimethyl. A liquid composition (r-5) was prepared in the same manner as in Example 1 except that amino-1- (4-morpholinophenyl) butan-1-one was changed to 50 parts by weight. A coating was formed on top.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was not completely dissolved, and a large amount of foreign matter was observed in the liquid.

Comparative Example 2
Instead of the solution (S-1), the solution (S-5) was used in such an amount that the copolymer (S-5) was 70 parts by weight, and (D) the photopolymerization initiator was 2-benzyl-2-dimethyl. A liquid composition (r-6) was prepared in the same manner as in Example 1 except that the amount was changed to 50 parts by weight of amino-1- (4-morpholinophenyl) butan-1- one, and a soda glass substrate was prepared. A coating was formed on top.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Comparative Example 3
Instead of the solution (S-1), the solution (S-6) was used in such an amount that the copolymer (S-6) was 70 parts by weight, and (D) the photopolymerization initiator was 2-benzyl-2-dimethyl. A liquid composition (r-7) was prepared in the same manner as in Example 1 except that the amount was changed to 50 parts by weight of amino-1- (4-morpholinophenyl) butan-1- one, and a soda glass substrate was prepared. A coating was formed on top.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference example 4
(A) C.I. I. Pigment blue 15: 6 and C.I. I. Diamond Fine Mill (trade name) was prepared by mixing 40 parts by weight of a 90/10 (weight ratio) mixture with Pigment Violet 23, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent. A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation. Next, 100 parts by weight of this pigment dispersion, (B) the solution (S-1) as an alkali-soluble resin, the amount that the copolymer (S-1) is 80 parts by weight, and (C) the polyfunctional monomer 70 parts by weight of dipentaerythritol hexaacrylate, (D) 30 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator, and propylene glycol monomethyl as a solvent 1,000 parts by weight of ether acetate was mixed to prepare a liquid composition (b-1).
Next, the liquid composition (b-1) is spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and then is subjected to 12 in a clean room at 23 ° C. A coating film was formed by drying after standing for a period of time.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference Example 5
The liquid composition (S-2) was replaced with the liquid composition (S-2) in the same manner as in Reference Example 4 , except that the copolymer (S-2) was used in an amount of 80 parts by weight. b-2) was prepared and a coating film was formed on a soda glass substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference Example 6
The liquid composition (S-3) was replaced with the liquid composition (S-3) in the same manner as in Reference Example 4 , except that the copolymer (S-3) was used in an amount of 80 parts by weight. b-3) was prepared, and a coating film was formed on a soda glass substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Example 2
(A) C.I. I. Pigment blue 15: 6 and C.I. I. Diamond Fine Mill (trade name) was prepared by mixing 40 parts by weight of a 90/10 (weight ratio) mixture with Pigment Violet 23, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent. A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation. Next, 100 parts by weight of this pigment dispersion, (B) the solution (S-1) as an alkali-soluble resin, the amount that the copolymer (S-1) is 80 parts by weight, and (C) the polyfunctional monomer 70 parts by weight of dipentaerythritol hexaacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl as a photopolymerization initiator } -9. H. -Carbazole-3-i] -1- (O-acetyloxime) 50 parts by weight and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (b-4) .
Next, the liquid composition (b-4) is spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface. A coating film was formed by drying after standing for a period of time .
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Comparative Example 4
Instead of the solution (S-1), the solution (S-4) was used in an amount such that the copolymer (S-4) was 80 parts by weight, and (D) the photopolymerization initiator was 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one A liquid composition (b-5) was prepared in the same manner as in Example 2 except that the amount was changed to 30 parts by weight. A coating film was formed on the substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was not completely dissolved, and a large amount of foreign matter was observed in the liquid.

Comparative Example 5
Instead of the solution (S-1), the solution (S-5) was used in such an amount that the copolymer (S-5) was 80 parts by weight, and (D) the photopolymerization initiator was 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one A liquid composition (b-6) was prepared in the same manner as in Example 2 except that the amount was changed to 30 parts by weight. A coating film was formed on the substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Comparative Example 6
Instead of the solution (S-1), the solution (S-6) was used in an amount such that the copolymer (S-6) was 80 parts by weight, and (D) the photopolymerization initiator was 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one A liquid composition (b-7) was prepared in the same manner as in Example 2 except that the amount was changed to 30 parts by weight. A coating film was formed on the substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference Example 7
(A) C.I. I. Pigment Green 36 and C.I. I. A mixture of 40 parts by weight of a 50/50 (weight ratio) mixture with Pigment Yellow 150, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was added to Diamond Fine Mill (trade name, A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) the solution (S-1) as an alkali-soluble resin, the amount that the copolymer (S-1) is 80 parts by weight, and (C) the polyfunctional monomer 70 parts by weight of dipentaerythritol hexaacrylate, (D) 30 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator, and propylene glycol monomethyl as a solvent 1,000 parts by weight of ether acetate was mixed to prepare a liquid composition (g-1).
Next, the liquid composition (g-1) was spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface. A coating film was formed by drying for a period of time.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference Example 8
The liquid composition (S-2) was replaced with the liquid composition (S-2) in the same manner as in Reference Example 7 , except that the copolymer (S-2) was used in an amount of 80 parts by weight. g-2) was prepared, and a coating film was formed on a soda glass substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Reference Example 9
The liquid composition (S-3) was replaced with the liquid composition (S-3) in the same manner as in Reference Example 7 , except that the copolymer (S-3) was used in an amount of 80 parts by weight. g-3) was prepared, and a coating film was formed on a soda glass substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Example 3
(A) C.I. I. Pigment Green 36 and C.I. I. A mixture of 40 parts by weight of a 50/50 (weight ratio) mixture with Pigment Yellow 150, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was added to Diamond Fine Mill (trade name, A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) the solution (S-1) as an alkali-soluble resin, the amount that the copolymer (S-1) is 80 parts by weight, and (C) the polyfunctional monomer 70 parts by weight of dipentaerythritol hexaacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl as a photopolymerization initiator } -9. H. -Carbazole-3-i] -1- (O-acetyloxime) 50 parts by weight and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (g-4) .
Next, the liquid composition (g-4) was spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface. A coating film was formed by drying for a period of time .
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Comparative Example 7
Instead of the solution (S-1), the solution (S-4) was used in an amount such that the copolymer (S-4) was 80 parts by weight , and (D) the photopolymerization initiator was 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one A liquid composition (g-5) was prepared in the same manner as in Example 3 except that the amount was changed to 30 parts by weight. A coating film was formed on the substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was not completely dissolved, and a large amount of foreign matter was observed in the liquid.

Comparative Example 8
Instead of the solution (S-1), the solution (S-5) was used in such an amount that the copolymer (S-5) was 80 parts by weight, and (D) the photopolymerization initiator was 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one A liquid composition (g-6) was prepared in the same manner as in Example 3 except that the amount was changed to 30 parts by weight. A coating film was formed on the substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Comparative Example 9
Instead of the solution (S-1), the solution (S-6) was used in an amount such that the copolymer (S-6) was 80 parts by weight, and (D) the photopolymerization initiator was 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one A liquid composition (g-7) was prepared in the same manner as in Example 3 except that the amount was changed to 30 parts by weight. A coating film was formed on the substrate.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Evaluation of voltage holding ratio
Reference Example 1 0
The soda glass in which the liquid composition (r-1) prepared in Example 1 is formed with a SiO ₂ film for preventing elution of sodium ions on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After spin coating on the substrate, pre-baking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 250 ° C. for 30 minutes. And the coating film was cured to form red pixels on the substrate. The film thickness of this pixel was 1.60 μm.
Next, the substrate on which this pixel is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then a liquid crystal MLC6608 (trade name) manufactured by Merck is used. The liquid crystal cell was manufactured by pouring.
Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica Co., Ltd. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). As a result, the voltage holding ratio was 95%.
When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-1) is less likely to cause “burn-in”.

Reference Example 1 1
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 2 (r-2) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-2) is less likely to cause “burn-in”.

Reference Example 1 2
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 3 (r-3) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-3) is less likely to cause “burn-in”.

Example 4
Soda glass in which the liquid composition (r-4) prepared in Example 1 is formed with a SiO ₂ film on its surface to prevent elution of sodium ions , and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After spin coating on the substrate, pre-baking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² without using a photomask . Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 250 ° C. for 30 minutes. And the coating film was cured to form red pixels on the substrate. The film thickness of this pixel was 1.60 μm.
Next, the substrate on which this pixel is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then a liquid crystal MLC6608 (trade name) manufactured by Merck is used. The liquid crystal cell was manufactured by pouring .
Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica Co., Ltd. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). As a result, the voltage holding ratio was 99%.
When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (r-4) has almost no risk of “burn-in”.

Comparative Example 10
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (r-5) prepared in Comparative Example 1 was used instead of the liquid composition (r- 4 ), and the voltage holding ratio was Was 94%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-5) is less likely to cause “burn-in”.

Comparative Example 11
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (r-6) prepared in Comparative Example 2 was used instead of the liquid composition (r -4 ), and the voltage holding ratio was Was 45%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-6) has a high possibility of causing “burn-in”.

Comparative Example 12
Instead of the liquid composition (r -4), except for using a liquid composition prepared in Comparative Example 3 (r-7), in the same manner as in Example 4, to prepare a liquid crystal cell, the voltage holding ratio Was measured to be 95%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-7) is less likely to cause “burn-in”.

Reference Example 1 3
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 4 (b-1) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (b-1) is less likely to cause “burn-in”.

Reference Example 1 4
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 5 (b-2) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (b-2) is less likely to cause “burn-in”.

Reference Example 1 5
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 6 (b-3) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (b-3) is less likely to cause “burn-in”.

Example 5
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (b-4) prepared in Example 2 was used instead of the liquid composition (r -4 ), and the voltage holding ratio was Was measured to be 98%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (b-4) has almost no risk of “burn-in”.

Comparative Example 13
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (b-5) prepared in Comparative Example 4 was used instead of the liquid composition (r -4 ), and the voltage holding ratio was Was 94%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (b-5) is less likely to cause “burn-in”.

Comparative Example 14
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (b-6) prepared in Comparative Example 5 was used instead of the liquid composition (r -4 ), and the voltage holding ratio was Was 45%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (b-6) is likely to cause “burn-in”.

Comparative Example 15
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (b-7) prepared in Comparative Example 6 was used in place of the liquid composition (r -4 ), and the voltage holding ratio was Was measured to be 95%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (b-7) is less likely to cause “burn-in”.

Reference Example 16
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 7 (g-1) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (g-1) is less likely to cause “burn-in”.

Reference Example 17
Instead of the liquid composition (r-1), except that the liquid composition prepared in Reference Example 8 (g-2) was used, in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (g-2) is less likely to cause “burn-in”.

Reference Example 18
Instead of the liquid composition (r-1), except for using a liquid composition prepared in Reference Example 9 (g-3), in the same manner as in Reference Example 1 0, to prepare a liquid crystal cell, the voltage retention When the rate was measured, it was 94%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (g-3) is less likely to cause “burn-in”.

Example 6
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (g-4) prepared in Example 3 was used instead of the liquid composition (r -4 ), and the voltage holding ratio was Was 99%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (g-4) has almost no risk of “burn-in”.

Comparative Example 16
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (g-5) prepared in Comparative Example 7 was used in place of the liquid composition (r -4 ), and the voltage holding ratio was Was 94%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (g-5) is less likely to cause “burn-in”.

Comparative Example 17
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (g-6) prepared in Comparative Example 8 was used in place of the liquid composition (r -4 ), and the voltage holding ratio was Was 45%. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (g-6) is likely to cause “burn-in”.

Comparative Example 18
A liquid crystal cell was produced in the same manner as in Example 4 except that the liquid composition (g-7) prepared in Comparative Example 9 was used instead of the liquid composition (r -4 ), and the voltage holding ratio was Was measured to be 95%. Therefore, the liquid crystal display device including the color filter formed using the liquid composition (g-7) is less likely to cause “burn-in”.

Evaluation of uneven color
Reference Example 19
Using the liquid composition (r-1) prepared in Reference Example 1, a coating film was formed on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air dried to form a coating.
Next, when the surface of the coating was observed using an optical microscope, no color unevenness was observed.

Reference Example 2 0
A film was formed in the same manner as in Reference Example 19 except that the liquid composition (r-2) prepared in Reference Example 2 was used instead of the liquid composition (r-1), and the surface of the film was observed with an optical microscope. When observed using, no color unevenness was observed.

Reference Example 2 1
A film was formed in the same manner as in Reference Example 19 except that the liquid composition (r-3) prepared in Reference Example 3 was used instead of the liquid composition (r-1), and the surface of the film was observed with an optical microscope. When observed using, no color unevenness was observed.

Example 7
A coating film was formed on a soda glass substrate using the liquid composition (r-4) prepared in Example 1 .
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask . Then immersed for 1 minute in a developing solution comprising the substrate from 0.04 wt% aqueous potassium hydroxide 23 ° C., then the developed, and air-dried and washed with ultrapure water to form a film.
Next , when the surface of the coating was observed using an optical microscope, no color unevenness was observed.

Comparative Example 19
A film was formed in the same manner as in Example 7 except that the liquid composition (r-5) prepared in Comparative Example 1 was used instead of the liquid composition (r -4 ), and the surface of the film was observed with an optical microscope. When observed using, no color unevenness was observed.

Comparative Example 20
A film was formed in the same manner as in Example 7 except that the liquid composition (r-6) prepared in Comparative Example 2 was used in place of the liquid composition (r -4 ). When observed using, no color unevenness was observed.

Comparative Example 21
A film was formed in the same manner as in Example 7 except that the liquid composition (r-7) prepared in Comparative Example 3 was used instead of the liquid composition (r -4 ), and the surface of the film was observed with an optical microscope. When observed using, color unevenness was observed.
Color unevenness is observed, which is likely to cause traffic jams in the foreign matter inspection machine in the color filter manufacturing process and reduce the product yield.

The main results are shown in Table 1.
In Table 1, “polymerization form” is a polymerization method for producing a copolymer, “living” means “living radical polymerization”, and “radical” means “radical polymerization”. In addition, “◯” in “solvent re-solubility” means that the coating film was completely dissolved, and “x” means that a large amount of foreign matter was observed in the liquid.

Claims (7)

A radiation-sensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (B) the alkali-soluble resin is (B1) one type selected from the group of unsaturated carboxylic acids or acid anhydrides and unsaturated phenol compounds, and (b2) a compound having an allyl group and another polymerizable unsaturated bond as a polymerizable unsaturated bond ; (B3) A copolymer with an unsaturated compound other than the above, and polystyrene measured by gel permeation chromatography (GPC) and polystyrene measured by gel permeation chromatography (GPC). The ratio (Mw / Mn) to the converted number average molecular weight (Mn) is 1.0 to 2.0, and (D) the photopolymerization initiator is an essential component of the carbazole compound. The radiation-sensitive resin composition characterized by a.   (B) The radiation-sensitive resin composition according to claim 1, wherein the alkali-soluble resin is a copolymer produced through a step of living radical polymerization. (D), wherein the carbazole compound is an essential component of the photopolymerization initiator is a compound represented by the compound and / or formula represented by the following formula (23) (24), according to claim 1 or The radiation sensitive resin composition of Claim 2.

[In the formula (23), R ³ 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 ⁴ and R ⁵ 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 ⁶ 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 ⁶ may be the same as or different from each other, and R ⁷ 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 ⁷ 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 (24), R ³ 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 ⁴ and R ⁵ 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 ⁶ 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 ⁶ may be the same as or different from each other, and R ⁷ 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 ⁷ 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. ]   (A) The colorant is a pigment, and a pigment dispersion obtained by mixing and dispersing the pigment in a solvent in the presence of a dispersant is mixed (B) alkali-soluble resin, (C) polyfunctional The method for preparing a radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the monomer and (D) a photopolymerization initiator are mixed. The radiation sensitive resin composition in any one of Claims 1-3 which is an object for color filters.   A color filter formed using the radiation-sensitive resin composition according to claim 5.   A color liquid crystal display device comprising the color filter according to claim 6.