KR20040079322A - Radiation sensitive composition for color filters - Google Patents

Abstract

PURPOSE: A radiation sensitive composition for use in a color filter is provided to drastically reduce the tact time by not generating the residual and stain on the substrate and the blind layer during the development. CONSTITUTION: A radiation sensitive composition for use in a color filter includes a coloring material, an alkali soluble resin, a multi-functional monomer and a photopolymerization initiator. The alkali soluble resin is made of an N-(3,5-demethyl-4-hydroxyphenyl)maleimide, N-p-carboxyphenylmaleimide, N-p-hydroxyphenyl(mat)acrylamide or p-hydroxyphenyl(mat)acrylrate and other unsaturated monomer or N-o-hydroxyphenylimide, N-m-hydroxyphenylimide or N-p-hydroxyphenylmaleimide and the other specific unsaturated monomer.

Description

Radiation-sensitive composition for color filters {RADIATION SENSITIVE COMPOSITION FOR COLOR FILTERS}

The present invention relates to a radiation sensitive composition for color filters used to form color filters for use in color liquid crystal display devices and imaging tube elements.

When manufacturing a color filter using a radiation sensitive composition so far, the radiation sensitive composition is apply | coated and dried on a board | substrate or the board | substrate which formed the light shielding layer of a predetermined pattern, and obtained the dried coating film, and this coating film The pixels of each color are obtained by exposing and developing in a predetermined pattern. In the color filter formed as described above, residues or stains tend to be formed on the substrate or the light shielding layer of the unexposed part at the time of development, and the adhesion of the pixel formed on the exposed part to the substrate or the light shielding layer is not sufficient, and the baked pixel after development There is a problem that the physical properties of the coating film is inferior.

Recently, photopolymerizable compositions containing (1) a photopolymerization initiator, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) a copolymer of an N-substituted maleimide monomer with another copolymerizable monomer are heat resistant. It has recently been disclosed that a color filter having excellent developer resistance, alkali resistance and substrate adhesion can be formed (JP-A No. 10-300922) (the term "JP-A" as used herein is referred to as a "Japanese patent Application publication ".

However, shortening of the tact time (development time) has been required to reduce the manufacturing cost, and the radiation property for color filters is improved compared to the composition disclosed in the above publication and other characteristics as color filters are also excellent. There is a strong demand for compositions.

An object of this invention is to provide the radiation sensitive composition for color filters which has the outstanding alkali developability.

According to the present invention, no residue or unevenness is generated on the substrate and the light shielding layer of the unexposed portion during alkali development, and the tact time can be shortened remarkably, and a novel high-definition and high-quality pixel can be formed with high efficiency. Another object is to provide a radiation sensitive composition for one color filter.

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

According to the present invention, the above objects and advantages of the present invention,

(A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator,

(B) alkali-soluble resin

(B1) an air of at least one unsaturated compound selected from the group consisting of N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester and other ethylenically unsaturated monomers copolymerizable with this unsaturated compound As a coalescing, the N-substituted maleimide is a phenyl group substituted with a hydrogen atom in the imide group of maleimide by (a1) a hydroxyl group, a carboxyl group, or both, or (a2) a hydroxyl group, a carboxyl group, or both. A compound obtained by substituting a cyclohexyl group substituted by c (excluding N- (monohydroxyphenyl) maleimide), wherein the N-substituted (meth) acrylamide is contained in an amide group of (meth) acrylamide. One hydrogen atom is substituted with a phenyl group substituted by (b1) a hydroxyl group, a carboxyl group, or both, or a cyclohexyl group substituted by (b2) a hydroxyl group, a carboxyl group, or both The (meth) acrylic acid ester is a phenyl group substituted with a hydrogen atom in the carboxyl group of (meth) acrylic acid by a (c1) hydroxyl group, a carboxyl group, or both, or (c2) a hydroxyl group or a carboxyl group. Or a copolymer which is a compound obtained by substituting a cyclohexyl group substituted by both;

(B2) 1 selected from the group consisting of (1) N- (monohydroxyphenyl) maleimide, (2) said N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester At least one unsaturated compound (excluding N- (monohydroxyphenyl) maleimide), (3) a copolymer of said other ethylenically unsaturated monomer; And

(B3) (1) N- (monohydroxyphenyl) maleimide, (2) (meth) acrylic acid, (3) styrene and (4) methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, macromonomers having a mono (meth) acryloyl group at the ends of the polymer molecular chains of polystyrene and polymethyl (meth) acrylates Copolymer of at least one (meth) acrylic acid ester selected from the group consisting of macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain of

It is achieved with a radiation sensitive composition for color filters, characterized in that it is selected from.

As used herein, the term "radiation" refers to visible light, ultraviolet light, far ultraviolet rays, electron beams and X-rays.

The present invention is described in detail below.

(A) colorant

The colorant used in the present invention is not particularly limited in color, but is appropriately selected depending on the application purpose of the color filter obtained. Both organic and inorganic colorants are possible.

Organic colorants are, for example, organic pigments, dyes or natural pigments. Inorganic colorants are, for example, inorganic salts referred to as inorganic pigments or "constitution pigments". Since a color filter requires high definition color and heat resistance, in this invention, the coloring agent which has high color development and high heat resistance, such as an organic coloring agent, and especially high thermal decomposition resistance is preferable, and an organic pigment is especially preferable.

Examples of the organic pigments include compounds classified into pigment groups according to the color index (C.I .; issued by The Society of Dyers and Colorists), and specifically, compounds having the following color index (C.I.) numbers.

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

C.I. Pigment Orange 36, C.I. Pigment Orange 43, C.I. Pigment Orange 51 and C.I. Pigment Orange 71:

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 215, C.I. Pigment Red 224, C.I. Pigment Red 242 and C.I. Pigment red 254;

C.I. Pigment Violet 19, C.I. Pigment violet 23 and C.I. Pigment violet 29;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3 and C.I. Pigment blue 15: 6;

C.I. Pigment Green 7 and C.I. Pigment green 36;

C.I. Pigment Brown 23 and C.I. Pigment brown 25; And

C.I. Pigment Black 1, C.I. Pigment Black 7.

Examples of inorganic colorants include titanium oxide, barium sulfate, zinc white, lead sulfate, chromium yellow, zinc sulfur, red iron oxide (iron red oxide (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, Amber, titanium black, synthetic iron black and carbon black.

Optionally, the colorant may be surface modified with a polymer prior to use.

In this invention, the said coloring agent can be used individually or in combination of 2 or more types.

Optionally, the colorant can be used in combination with a dispersant.

Dispersants are cationic, anionic, nonionic, zwitterionic, silicone-based or fluorine-based surfactants.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid-modified polyesters; Tertiary amine-modified polyurethanes; And polyethylene imines. Such surfactants are trade name KP (manufactured by Shin-Etsu Chemical, Co., Ltd.), polyflow (Kyoeisha Yushi Kagaku Co., Ltd.) F-Top (manufactured by Token Products Co., Ltd.), Mega Pack (manufactured by Dainippon Ink and Chemicals, Inc.), Florade (Sumitomo 3M Corporation) Manufactured by Sumitomo 3M Limited), manufactured by Asahi Guard and Supron (manufactured by Asahi Glass Co., Ltd.), manufactured by EFKA (EFKA Chemicals Beefy Co., Ltd.) ), Disparon (manufactured by Tsukamoto Kasei Co., Ltd.), Dispervic and BYK (manufactured by Byk Chemie Japan Co., Ltd.), and Solsper (Geneva) (Manufactured by Zenca Co., Ltd.) can be used.

These surfactants can be used alone or in combination of two or more thereof.

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

(B) alkali soluble resin

The alkali-soluble resin of the present invention is selected from the following copolymers (B1), (B2) and (B3).

(B1) The copolymer is at least one unsaturated compound selected from the group consisting of N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester, and other ethylenically unsaturated copolymerizable with this compound. Copolymers of monomers. Said N-substituted maleimide is selected from a hydrogen atom in the imide group of maleimide by (a1) a phenyl group substituted by a hydroxyl group, a carboxyl group, or both, or (a2) a hydroxyl group, a carboxyl group, or both. Compounds obtained by substitution with a substituted cyclohexyl group (excluding N- (monohydroxyphenyl) maleimide). The N-substituted (meth) acrylamide is a phenyl group substituted with one hydrogen atom in the amide group of (meth) acrylamide by (b1) a hydroxyl group, a carboxyl group, or both, or (b2) a hydroxyl group. , And a compound obtained by substituting a cyclohexyl group substituted by a carboxyl group or both. The (meth) acrylic acid ester is a phenyl group substituted with a (c1) hydroxyl group, a carboxyl group, or both by a hydrogen atom in a carboxyl group of (meth) acrylic acid, or (c2) a hydroxyl group, a carboxyl group, or both. A compound obtained by substituting a substituted cyclohexyl group.

Component (B2) is selected from the group consisting of (1) N- (monohydroxyphenyl) maleimide, (2) said N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester At least one unsaturated compound (excluding N- (monohydroxyphenyl) maleimide), and (3) a copolymer of said other ethylenically unsaturated monomer.

Component (B3) comprises (1) N- (monohydroxyphenyl) maleimide, (2) (meth) acrylic acid, (3) styrene and (4) methyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, macromonomer and polymethyl (meth) having a mono (meth) acryloyl group at the end of the polymer molecular chain of polystyrene It is a copolymer of 1 or more types of (meth) acrylic acid ester chosen from the group which consists of a macromonomer which has a mono (meth) acryloyl group at the terminal of the polymer molecular chain of an acrylate.

The phenyl group and cyclohexyl group contained in the N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester in the copolymers (B1) and (B2) constitute a phenyl group and a cyclohexyl group. It may further have substituents other than a hydroxyl group and a carboxyl group at each carbon atom. Examples of the substituent include halogen atoms (fluorine atom, chlorine atom and bromine atom, etc.), (cyclo) alkyl groups having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and t- Butyl group), (cyclo) alkylcarbonyloxy group having 2 to 10 carbon atoms (methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n- Butylcarbonyloxy group and t-butylcarbonyloxy group, etc.), (cyclo) alkoxycarbonyl group having 2 to 10 carbon atoms (methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n- Butoxycarbonyl group, t-butoxycarbonyl group, and the like).

Among these substituents, a methyl group, an ethyl group, a methylcarbonyloxy group, an ethylcarbonyloxy group, a methoxycarbonyl group and an ethoxycarbonyl group are preferable.

N-substituted maleimide in (B1) alkali-soluble resin and (B2) alkali-soluble resin is N-substituted maleimide other than N- (monohydroxyphenyl) maleimide. Examples of N-substituted maleimides include

N- (2,6-dimethyl-4-hydroxyphenyl) maleimide,

N- (3,5-dimethyl-4-hydroxyphenyl) maleimide,

N- (2,4-dihydroxyphenyl) maleimide,

N- (3,5-dihydroxyphenyl) maleimide,

N-p-carboxyphenylmaleimide,

N- (2,4-dicarboxyphenyl) maleimide,

N- (3,5-dicarboxyphenyl) maleimide,

N- (2-hydroxy-4-carboxyphenyl) maleimide,

N-o-hydroxycyclohexylmaleimide,

N-m-hydroxycyclohexylmaleimide,

N-p-hydroxycyclohexylmaleimide,

N- (2,6-dimethyl-4-hydroxycyclohexyl) maleimide,

N- (3,5-dimethyl-4-hydroxycyclohexyl) maleimide,

N- (2,4-dihydroxycyclohexyl) maleimide,

N- (3,5-dihydroxycyclohexyl) maleimide,

N-p-carboxycyclohexylmaleimide,

N- (2,4-dicarboxycyclohexyl) maleimide,

N- (3,5-dicarboxycyclohexyl) maleimide and

N- (2-hydroxy-4-carboxycyclohexyl) maleimide.

Among the N-substituted maleimides,

N- (2,6-dimethyl-4-hydroxyphenyl) maleimide,

N- (3,5-dimethyl-4-hydroxyphenyl) maleimide,

N- (3,5-dihydroxyphenyl) maleimide,

N-p-carboxyphenylmaleimide,

N- (3,5-dicarboxyphenyl) maleimide,

N-p-hydroxycyclohexylmaleimide,

N- (3,5-dihydroxycyclohexyl) maleimide,

N-p-carboxycyclohexylmaleimide and

N- (3,5-dicarboxycyclohexyl) maleimide is preferred.

The said N-substituted maleimide can be used individually or in combination of 2 or more types.

Examples of N-substituted (meth) acrylamides include No-hydroxyphenyl (meth) acrylamide, Nm-hydroxyphenyl (meth) acrylamide, Np-hydroxyphenyl (meth) acrylamide, N- (2, 6-dimethyl-4-hydroxyphenyl) (meth) acrylamide, N- (3,5-dimethyl-4-hydroxyphenyl) (meth) acrylamide, N- (2,4-dihydroxyphenyl) ( Meth) acrylamide, N- (3,5-dihydroxyphenyl) (meth) acrylamide, Np-carboxyphenyl (meth) acrylamide, N- (3,5-dicarboxyphenyl) (meth) acrylamide, N- (2-hydroxy-4-carboxyphenyl) (meth) acrylamide, No-hydroxycyclohexyl (meth) acrylamide, Nm-hydroxycyclohexyl (meth) acrylamide, Np-hydroxycyclohexyl ( Meth) acrylamide, N- (2,6-dimethyl-4-hydroxycyclohexyl) (meth) acrylamide, N- (3,5-dimethyl-4-hydroxycyclohexyl) (meth) acrylamide, N -(2,4-dihydroxycyclohex (Meth) acrylamide, N- (3,5-dihydroxycyclohexyl) (meth) acrylamide, Np-carboxycyclohexyl (meth) acrylamide, N- (3,5-dicarboxycyclohexyl) ( Meth) acrylamide and N- (2-hydroxy-4-carboxycyclohexyl) (meth) acrylamide.

Np-hydroxyphenyl (meth) acrylamide, N- (3,5-dihydroxyphenyl) (meth) acrylamide, Np-carboxyphenyl (meth) acrylamide in the said N-substituted (meth) acrylamides , N- (3,5-dicarboxyphenyl) (meth) acrylamide, Np-hydroxycyclohexyl (meth) acrylamide, N- (3,5-dihydroxycyclohexyl) (meth) acrylamide, Np -Carboxycyclohexyl (meth) acrylamide and N- (3,5-dicarboxycyclohexyl) (meth) acrylamide are preferred.

The said N-substituted (meth) acrylamides can be used individually or in combination of 2 or more types.

Examples of (meth) acrylic acid esters include o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl (meth) acrylate, 2,6-dimethyl-4-hydroxy Hydroxyphenyl (meth) acrylate, 3,5-dimethyl-4-hydroxyphenyl (meth) acrylate, 2,4-dihydroxyphenyl (meth) acrylate, 3,5-dihydroxyphenyl (meth) Acrylate, p-carboxyphenyl (meth) acrylate, 3,5-dicarboxyphenyl (meth) acrylate, 2-hydroxy-4-carboxyphenyl (meth) acrylate, o-hydroxycyclohexyl (meth) Acrylate, m-hydroxycyclohexyl (meth) acrylate, p-hydroxycyclohexyl (meth) acrylate, 2,6-dimethyl-4-hydroxycyclohexyl (meth) acrylate, 3,5-dimethyl 4-hydroxycyclohexyl (meth) acrylate, 2,4-dihydroxycyclohexyl (meth) acrylate, 3,5-dihydroxyoxy Lohexyl (meth) acrylate, p-carboxycyclohexyl (meth) acrylate, 3,5-dicarboxycyclohexyl (meth) acrylate and 2-hydroxy-4-carboxycyclohexyl (meth) acrylate do.

Among these (meth) acrylic acid esters, p-hydroxyphenyl (meth) acrylate, 3,5-dihydroxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, 3,5-dicarboxyphenyl ( Meth) acrylate, p-hydroxycyclohexyl (meth) acrylate, 3,5-dihydroxycyclohexyl (meth) acrylate, p-carboxycyclohexyl (meth) acrylate and 3,5-dicarboxycyclo Hexyl (meth) acrylate is preferred.

The said (meth) acrylic acid ester can be used individually or in combination of 2 or more types.

When the other copolymerizable ethylenically unsaturated monomer in (B1) alkali-soluble resin and (B2) alkali-soluble resin can copolymerize with N-substituted maleimide, N-substituted (meth) acrylamide, and (meth) acrylic acid ester It is not specifically limited. Ethylenically unsaturated monomers are ethylenically unsaturated monomers having one or more carboxyl groups (called "other carboxyl-containing unsaturated monomers") and other ethylenically unsaturated monomers copolymerizable with said monomers (hereinafter abbreviated as "other unsaturated monomers") It is preferable that it is a mixture with.

Examples of other carboxyl group-containing unsaturated monomers include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, ω-carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acrylo Unsaturated monocarboxylic acids such as monooxyethyl succinic acid; Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; And unsaturated polycarboxylic acids (anhydrides) having three or more carboxyl groups.

These other carboxyl group-containing unsaturated monomers may be used alone or in combination of two or more thereof.

Examples of other unsaturated monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene aromatic vinyl compounds such as p-vinylbenzylmethyl ether and p-vinylbenzyl glycidyl ether; Indenes such as indene and 1-methylindene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl ( Unsaturated carboxylates such as meth) acrylate, methoxytriethylene glycol (meth) acrylate and glycerol mono (meth) acrylate; Unsaturated aminoalkyl carboxylates such as 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate and 3-aminopropyl (meth) acrylate; Unsaturated glycidyl carboxylates such as glycidyl (meth) acrylate; Vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate: unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and metalryl glycidyl ether; Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

These other unsaturated monomers can be used individually or in combination of 2 or more types.

The other copolymerizable ethylenically unsaturated monomer in (B1) alkali-soluble resin and (B2) alkali-soluble resin is (i) at least one unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid, or unsaturated acid and ω-carboxypolycaprol A combination with at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of lactone mono (meth) acrylate and 2- (meth) acryloyloxyethylsuccinic acid, (ii) styrene, and (iii) methyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macro monomers and polymethylmethacrylate macro monomers A mixture with at least one selected from the group consisting of is preferred.

(B1) In the alkali-soluble resin, the amount of at least one unsaturated compound selected from the group consisting of N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester is preferably 5 to 50% by weight. %, More preferably, it is 10-40 weight%.

When the amount is less than 5% by weight, the heat resistance of the obtained pixel may be lowered, and when the amount is more than 50% by weight, alkali solubility of the obtained resin may deteriorate, and thus, on the substrate or the light shielding layer of the unexposed part Residues or stains may be produced.

When the other copolymerizable ethylenically unsaturated monomer is a mixture with other carboxyl group-containing unsaturated monomers and other unsaturated monomers, the amount of other carboxyl group-containing unsaturated monomers is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. %, And the amount of other unsaturated monomers becomes like this. Preferably it is 10 to 90 weight%, More preferably, it is 20 to 80 weight%.

When the amount of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility in the alkaline developer of the resulting composition may decrease, and when the amount is more than 50% by weight, the pixels formed at the time of development with the alkaline developer are removed from the substrate. Dropping or roughening of the pixel surface may occur.

In particular, the alkali-soluble resin (B1) containing a carboxyl group-containing unsaturated monomer in the above-mentioned specific amount is excellent in solubility with respect to an alkaline developer, and the radiation-sensitive composition containing the resin as a binder remains undissolved after development with an alkaline developer. Very little to do and little stain or film residue is produced in areas other than the part forming the pixels on the substrate. Moreover, the pixel obtained from this composition does not melt | dissolve excessively in alkaline developing solution, is excellent in adhesiveness with respect to a board | substrate, and does not fall off from a board | substrate.

(B2) a group consisting of (1) N- (monohydroxyphenyl) maleimide and (2) N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester in alkali-soluble resin The total amount of at least one unsaturated compound (excluding N- (monohydroxyphenyl) maleimide) selected from is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

If the amount is less than 5% by weight, the heat resistance of the resulting pixel may be lowered. If the amount is more than 50% by weight, alkali solubility of the obtained resin may deteriorate, and thus remain on the substrate or the light shielding layer of the unexposed part. It can produce water or stains.

When the other copolymerizable ethylenically unsaturated monomer (3) is a mixture with other carboxyl group-containing unsaturated monomers and other unsaturated monomers, the amount of other carboxyl group-containing unsaturated monomers is preferably 5 to 50% by weight, more preferably. Preferably it is 10 to 40 weight%, and the amount of other unsaturated monomers becomes like this. Preferably it is 10 to 90 weight%, More preferably, it is 20 to 80 weight%.

When the amount of the other carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility in the alkaline developer of the resulting composition may decrease, and when the amount is more than 50% by weight, the pixels formed at the time of development with the alkaline developer are substrates. May fall off or rough the pixel surface.

In particular, the alkali-soluble resin (B2) containing other carboxyl group-containing unsaturated monomers in the above specific amounts is excellent in solubility in alkaline developing solutions, and the radiation-sensitive composition containing the resin as a binder is cosmetically developed after development with an alkaline developing solution. It is very unlikely that the residue remains and hardly produces spots or film residues in areas other than the portions forming the pixels on the substrate. Moreover, the pixel obtained from this composition does not melt | dissolve excessively in alkaline developing solution, is excellent in adhesiveness with respect to a board | substrate, and does not fall off from a board | substrate.

The copolymer (B3) is composed of (1) N- (monohydroxyphenyl) maleimide, (2) (meth) acrylic acid, (3) styrene and (4) methyl (meth) acrylate, 2-hydroxyethyl ( Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, macromonomers having a mono (meth) acryloyl group at the ends of the polymer molecular chain of polystyrene and polymethyl ( It is a copolymer of 1 or more types of (meth) acrylic acid ester chosen from the group which consists of a macromonomer which has a mono (meth) acryloyl group at the terminal of the polymer molecular chain of meth) acrylate.

Examples of the (1) N- (monohydroxyphenyl) maleimide are N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide and N-p-hydroxyphenylmaleimide. These can be used individually or in combination of 2 or more types.

Examples of the (2) (meth) acrylic acid are acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used as said component (2) individually or in combination of 2 or more types.

One or more carboxyl group-containing ethylenically unsaturated monomers selected from the group consisting of ω-carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethylsuccinic acid, alone or in combination of two or more It can be used as component (2).

In the alkali-soluble resin (B3), the amount of (1) N- (monohydroxyphenyl) maleimide is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

If the amount is less than 5% by weight, the heat resistance of the resulting pixel may be lowered. If the amount is more than 50% by weight, alkali solubility of the obtained resin may deteriorate, and thus remain on the substrate or the light shielding layer of the unexposed part. It can produce water or stains.

(2) The amount of the combination of (meth) acrylic acid or (meth) acrylic acid with a carboxyl group-containing ethylenically unsaturated monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. (3) styrene and (4) methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macro The total amount of at least one (meth) acrylic acid ester selected from the group consisting of monomers and polymethyl (meth) acrylate macromonomers is preferably 10 to 90% by weight, more preferably 20 to 80% by weight. (3) The amount of styrene is preferably 5 to 30% by weight, more preferably 5 to 20% by weight.

(2) When the amount of the combination of (meth) acrylic acid or (meth) acrylic acid with a carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility in the alkaline developer of the resulting composition may decrease, and the amount is 50 In the case of more than% by weight, the formed pixel may be dropped from the substrate or the surface of the pixel may be rough when developing with an alkaline developer.

In particular, the alkali-soluble resin (B3) containing the specific amount of the component (2) is excellent in solubility in an alkaline developer, and the radiation-sensitive composition containing the resin as a binder is an alkali developer, in which undissolved residues remain after development. Are very few and produce little speckle or film residue in areas other than those forming pixels on the substrate. Moreover, the pixel obtained from this composition does not melt | dissolve excessively in alkaline developing solution, is excellent in adhesiveness with respect to a board | substrate, and does not fall off from a board | substrate.

Preferred examples of the alkali-soluble resin are as follows.

Examples of (B1) alkali-soluble resins include N- (2,6-dimethyl-4-hydroxyphenyl) maleimide, copolymers of (meth) acrylic acid, styrene and benzyl (meth) acrylate, and N- (3,5 -Dimethyl-4-hydroxyphenyl) maleimide, a copolymer of (meth) acrylic acid, styrene, benzyl (meth) acrylate and glycerol mono (meth) acrylate, Np-carboxyphenylmaleimide, (meth) acrylic acid, 2 Copolymers of-(meth) acryloyloxyethylsuccinic acid, styrene and benzyl (meth) acrylate, Np-hydroxycyclohexylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate , Copolymers of styrene and benzyl (meth) acrylate, and copolymers of Np-hydroxyphenyl (meth) acrylamide, (meth) acrylic acid, styrene and benzyl (meth) acrylate, Np-hydroxyphenyl (meth) Acrylate, (meth) acrylic acid, styrene, benzyl (meth) a Copolymers of acrylate and glycerol mono (meth) acrylates are included.

(B2) Examples of alkali-soluble resins include one or more selected from the group consisting of No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide, and No-hydroxyphenyl (meth). 1 or more types selected from the group consisting of acrylamide, Nm-hydroxyphenyl (meth) acrylamide and Np-hydroxyphenyl (meth) acrylamide, copolymers of styrene, (meth) acrylic acid and benzyl (meth) acrylate , At least one selected from the group consisting of No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide, No-carboxyphenylmaleimide, Nm-carboxyphenylmaleimide and Np- One or more selected from the group consisting of carboxyphenylmaleimide, styrene, (meth) acrylic acid, ω-carboxypolycaprolactone (meth) acrylate and benzyl (meth 1) at least one selected from the group consisting of copolymers of acrylate and No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide, o-hydroxyphenyl (meth) acrylic Styrene, (meth) acrylic acid, benzyl (meth) acrylate and glycerol (meth) selected from the group consisting of latex, m-hydroxyphenyl (meth) acrylate and p-hydroxyphenyl (meth) acrylate ) Copolymers of acrylates.

Examples of the (B3) alkali-soluble resin include at least one selected from the group consisting of No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene and benzyl At least one selected from the group consisting of copolymers of (meth) acrylates, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene and phenyl At least one selected from the group consisting of copolymers of (meth) acrylates, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, benzyl Copolymers of (meth) acrylate and glycerol mono (meth) acrylate, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmal At least one member selected from the group consisting of imides, copolymers of (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, styrene and benzyl (meth) acrylate, No-hydroxyphenylmaleimide, Nm- At least one selected from the group consisting of hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, styrene and benzyl (meth) acrylate At least one selected from the group consisting of copolymers of No, hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, benzyl (meth) acrylate And a copolymer of a polystyrene macromonomer, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide. At least one selected from the group consisting of copolymers of (meth) acrylic acid, styrene, benzyl (meth) acrylate and polymethyl methacrylate macromonomers, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np- 1 or more types selected from the group consisting of hydroxyphenylmaleimide, copolymers of (meth) acrylic acid, styrene, phenyl (meth) acrylate and polystyrene macromonomers, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide 1 or more types chosen from the group which consists of a mead and Np-hydroxyphenyl maleimide, the copolymer of (meth) acrylic acid, styrene, a phenyl (meth) acrylate, and a polymethyl methacrylate macromonomer, No-hydroxyphenyl maleim 1 or more types chosen from the group which consists of a mead, Nm-hydroxyphenyl maleimide, and Np-hydroxyphenyl maleimide, (meth) acrylic acid Copolymers of styrene, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and polystyrene macromonomers, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide At least one selected from the group consisting of meads, copolymers of (meth) acrylic acid, styrene, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and polymethyl methacrylate macromonomers, and no-hydride At least one selected from the group consisting of hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, 2-hydroxyethyl (meth) acrylate, phenyl ( Copolymers of meth) acrylates and polystyrene macromonomers, and No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide At least 1 type selected from the group which consists of a copolymer of (meth) acrylic acid, styrene, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, and a polymethyl methacrylate macromonomer is contained.

Among the alkali-soluble resins, particularly preferred are copolymers of N- (2,6-dimethyl-4-hydroxyphenyl) maleimide, (meth) acrylic acid, styrene and benzyl (meth) acrylate, N- (3,5 -Dimethyl-4-hydroxyphenyl) maleimide, a copolymer of (meth) acrylic acid, styrene, benzyl (meth) acrylate and glycerol mono (meth) acrylate, Np-carboxyphenylmaleimide, (meth) acrylic acid, 2 Copolymers of-(meth) acryloyloxyethylsuccinic acid, styrene and benzyl (meth) acrylate, Np-hydroxycyclohexylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate , Copolymer of styrene and benzyl (meth) acrylate, Np-hydroxyphenyl (meth) acrylamide, copolymer of (meth) acrylic acid, styrene and benzyl (meth) acrylate, Np-hydroxyphenyl (meth) acrylic Elate, (meth) acrylic acid, s Alkylene, benzyl (meth) acrylate and glycerol (B1) an alkali-soluble resin, such as mono (meth) acrylate copolymer; And copolymers of Nm-hydroxyphenylmaleimide, (meth) acrylic acid, styrene and benzyl (meth) acrylate, copolymers of Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene and benzyl (meth) acrylate , No-hydroxyphenylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, copolymer of styrene and benzyl (meth) acrylate, Np-hydroxyphenylmaleimide, (meth ) Acrylic acid, copolymer of 2- (meth) acryloyloxyethylsuccinic acid, styrene and benzyl (meth) acrylate, Np-hydroxyphenylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth ) Acrylates, copolymers of styrene and benzyl (meth) acrylates, and copolymers of Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, benzyl (meth) acrylates and glycerol mono (meth) acrylates (B3) alkali-soluble resin, such as these.

In the present invention, the alkali-soluble resins (B) may be used alone or in combination of two or more thereof.

In the present invention, one or more other alkali-soluble resins may be used in combination with alkali-soluble resins (B1) to (B3).

Examples of other alkali-soluble resins are resins having acidic functional groups such as carboxyl groups or phenolic hydroxyl groups.

Among other alkali-soluble resins, a resin having a carboxyl group (hereinafter referred to as "alkali-soluble resin (β-1)") is preferably a copolymer of the other carboxyl group-containing unsaturated monomer with the other unsaturated monomer, ) Acrylic acid and / or methacrylic acid and (ii) methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, polystyrene macro monomers and polymethyl methacrylate macro monomers More preferred is a copolymer with at least one member selected from the group consisting of:

Examples of alkali-soluble resin (β-1) include copolymers of (meth) acrylic acid and benzyl (meth) acrylate, copolymers with (meth) acrylic acid, methyl (meth) acrylate and styrene, (meth) acrylic acid and benzyl Copolymers of (meth) acrylate and styrene, copolymers of (meth) acrylic acid, methyl (meth) acrylate and polystyrene macromonomers, (meth) acrylic acid, methyl (meth) acrylate and polymethyl methacrylate macromonomers Copolymer of (meth) acrylic acid, benzyl (meth) acrylate and polystyrene macromonomer, copolymer of (meth) acrylic acid, benzyl (meth) acrylate and polymethyl methacrylate macromonomer, (meth) acrylic acid , Copolymers of 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and polystyrene macromonomers, and (meth) acrylic acid, 2-hydroxy (Meth) acrylate, benzyl (meth) acrylate and a copolymer of poly (methyl methacrylate) macromonomers.

The amount of the other alkali-soluble resin is preferably 50% by weight or less, more preferably 30% by weight or less based on the total amount of the alkali-soluble resin. When the amount of other alkali-soluble resin is more than 50 weight%, the heat resistance of the obtained pixel may fall.

Alkali-soluble resin in this invention contains as an essential component 1 or more types chosen from the group which consists of (B1) alkali-soluble resin, (B2) alkali-soluble resin, and (B3) alkali-soluble resin. The polystyrene reduced weight average molecular weight (hereinafter referred to simply as "weight average molecular weight") measured by gel permeation chromatography (GPC: the eluting solvent is tetrahydrofuran) of each component constituting the alkali-soluble resin is preferably 3,000. To 300,000, particularly preferably 5,000 to 100,000. By using an alkali-soluble resin having such a specific weight average molecular weight, a radiation-sensitive composition having excellent developability can be obtained, and a pixel having a sharp pattern edge can be formed from this composition, and the pixel on the substrate can be formed at the time of development. Almost no spots or film residues are produced in areas other than the forming part.

The content of the alkali-soluble resin in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight based on 100 parts by weight of the (A) colorant.

When the content of the alkali-soluble resin is less than 10 parts by weight, staining or film residue may be produced in a region other than a portion where alkali developability is lowered or a pixel is formed. When the content is more than 1,000 parts by weight, since the colorant concentration is relatively low, it may be difficult to achieve the desired color concentration as a thin film.

(C) polyfunctional monomer

Examples of the polyfunctional monomer in the present invention include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol, and dicarboxylic acid modified substances thereof; Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spiran resin; Di (meth) acryl of a polymer in which both ends are hydroxylated, such as polybutadiene having a hydroxyl group at both ends, polyisoprene having a hydroxyl group at both ends, and polycaprolactone having a hydroxyl group at both ends Rates; And tris (meth) acryloyloxyethyl phosphate.

Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups and their dicarboxylic acid modified substances are preferable, and trimethylolpropane tri (meth) acrylate and pentaerythritol Tri (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate can be exemplified. Trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol because of high pixel intensity, excellent smoothness of the pixel surface and little generation of spots or film residues in areas other than where the pixels are formed Hexaacrylate is particularly preferred.

The said functional monomer can be used individually or in combination of 2 or more types.

The content of the polyfunctional monomer in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the (B) alkali-soluble resin.

When the content of the polyfunctional monomer is less than 5 parts by weight, the pixel intensity and the smoothness of the surface of the pixel may be lowered. When the content is more than 500 parts by weight, the alkali developability is lowered or in a region other than the portion where the pixel is formed. It can produce stains or film residues.

In the present invention, a monofunctional monomer and a polyfunctional monomer can be used in combination.

Examples of monofunctional monomers include ω-carboxypolycaprolactone mono (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxy Propyl (meth) acrylate and 2- (meth) acryloyloxyethylsuccinic acid. A commercially available product, such as a brand name M-5300 (made by Toagosei Chemical Industry Co., Ltd.), can be used for a monofunctional monomer.

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

The content of the monofunctional monomer is preferably 0 to 90 parts by weight, more preferably 0 to 50 parts by weight, based on 100 parts by weight of the total weight of the polyfunctional monomer and the monofunctional monomer.

(D) photoinitiator

The photopolymerization initiator in the present invention is an activity capable of initiating polymerization with the (C) polyfunctional monomer and a monofunctional monomer used by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like. It is a compound capable of forming species. Examples of such photoinitiators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinine compounds, xanthone compounds and diazo compounds do.

In this invention, the said photoinitiator can be used individually or in combination of 2 or more types. It is preferable that a photoinitiator is 1 or more types chosen from the group which consists of an acetophenone type compound, a biimidazole type compound, and a triazine type compound.

The amount of the photopolymerization initiator in the present invention is preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight based on 100 parts by weight of the total weight of the (C) polyfunctional monomer and the monofunctional monomer (if used). to be.

When the amount of the photopolymerization initiator is less than 0.01 part by weight, it may be difficult to obtain a pixel array arranged in a predetermined pattern due to insufficient curing due to exposure, and when the amount exceeds 80 parts by weight, the formed colored layer is developed at the time of development. Easily detached from the substrate.

Examples of acetophenone-based compounds as preferred photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone and 2,2-dimethoxy-1,2-di Phenylethan-1-one.

Among these acetophenone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butan-1-one is particularly preferred.

The acetophenone compounds may be used alone or in combination of two or more thereof.

When using an acetophenone-based compound as the photopolymerization initiator, the amount of the acetophenone-based compound is preferably 0.01 to 80 parts by weight, more preferably 1 based on 100 parts by weight of the total weight of the polyfunctional monomer and the monofunctional monomer. To 60 parts by weight, more preferably 1 to 30 parts by weight.

When the amount of the acetophenone-based compound is less than 0.01 part by weight, it may be difficult to obtain a pixel array arranged in a predetermined pattern due to insufficient curing due to exposure, and when the amount exceeds 80 parts by weight, the formed colored layer is developed. It can be easily dropped from the substrate at the time.

Examples of biimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimi Dazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromo Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl- More preferred are 1,2'-biimidazole.

The non-imidazole-based compound is excellent in solubility in solvents and does not generate foreign matters such as undissolved products and precipitates, and has a high sensitivity and does a sufficient curing reaction even when exposed to a small amount of energy and does not cause a curing reaction in the unexposed part. Therefore, the coated film after exposure is clearly divided into a hardened portion insoluble to the developer and an uncured portion highly soluble to the developer, thereby forming a high-definition pixel array without finish cutting arranged in a predetermined pattern.

The said biimidazole type compound can be used individually or in combination of 2 or more types.

When using a biimidazole type compound as a photoinitiator, the amount of a biimidazole type compound is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total weight of the polyfunctional monomer and the monofunctional monomer. Is 1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

When the amount of the biimidazole compound is less than 0.01 part by weight, it may be difficult to obtain a pixel array arranged in a predetermined pattern due to insufficient curing due to exposure, and when the amount exceeds 40 parts by weight, the formed colored layer may It can be easily dropped from the substrate at the time of development.

-Hydrogen donor-

When using a biimidazole type compound as a photoinitiator in this invention, it is preferable to mix | blend with the following hydrogen donor for a sensitivity improvement.

As used herein, the term "hydrogen donor" refers to a compound capable of providing hydrogen atoms to radicals generated from biimidazole-based compounds by exposure.

The hydrogen donor in the present invention is preferably a mercaptan compound or an amine compound defined below.

The mercaptan compound has a benzene ring or a hetero ring as a mother nucleus, and a compound having one or more, preferably 1 to 3, more preferably 1 or 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 hetero ring as a parent nucleus, and having at least one, preferably 1 to 3, more preferably 1 or 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as "amine System hydrogen donor ".

The hydrogen donor may have a mercapto group and an amino group at the same time.

This hydrogen donor will then be described in detail.

The mercaptan-based hydrogen donor may have one or more benzene rings or hetero rings or both. If it has two or more rings, it may or may not form a condensed ring.

When the mercaptan-based hydrogen donor has two or more mercapto groups, one or more other mercapto groups may be substituted with alkyl, aralkyl or aryl groups as long as one or more free mercapto groups remain. Furthermore, as long as at least one free mercapto group remains, it may have a structural unit in which two sulfur atoms are bonded by a divalent organic group such as an alkylene group, or a structural unit in which two sulfur atoms are bonded to form disulfide.

In addition, the mercaptan-based hydrogen donor may be substituted at a position other than the mercapto group with a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group or nitrile group.

Examples of mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-2,5-dimethylaminopyridine is included.

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

The amine-based hydrogen donor may have one or more benzene rings or hetero rings or both. If it has two or more rings, it may or may not form a condensed ring.

One or more amino groups in the amine-based hydrogen donor may be substituted with an alkyl group or a substituted alkyl group, or the amine-based hydrogen donor may be substituted with a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, or substituted phenoxycarbonyl group Or a nitrile group.

Examples of the amine hydrogen donor include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoate and 4-dimethylaminobenzonitrile.

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

The amine hydrogen donor functions as a sensitizer for photopolymerization initiators other than the biimidazole compound.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. Since the formed colored layer hardly falls off the substrate at the time of development, and the strength and sensitivity of the colored layer are high, it is preferable to use a combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors.

Examples of combinations with mercaptan-based hydrogen donors and amine-based hydrogen donors include combinations with 2-mercaptobenzothiazole and 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole and 4 Combination with, 4'-bis (diethylamino) benzophenone, combination with 2-mercaptobenzoxazole and 4,4'-bis (dimethylamino) benzophenone, and 2-mercaptobenzoxazole And combinations with 4,4'-bis (diethylamino) benzophenone. Combination of 2-mercaptobenzothiazole and 4,4'-bis (diethylamino) benzophenone with combination of 2-mercaptobenzooxazole and 4,4'-bis (diethylamino) benzophenone Water is preferred, and combinations with 2-mercaptobenzothiazole and 4,4'-bis (diethylamino) benzophenone are particularly preferred.

The weight ratio of the mercaptan-based hydrogen donor to the amine-based hydrogen donor in combination with the mercaptan-based hydrogen donor and the amine-based hydrogen donor is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1: 1. 3

When using a hydrogen donor in combination with a biimidazole-based compound, the amount of the hydrogen donor is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total weight of the polyfunctional monomer and the monofunctional monomer. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity may be lowered, and when the amount exceeds 40 parts by weight, the formed colored layer may easily drop off from the substrate during development.

Examples of the triazine-based 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 (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6 Triazine type compounds which have halomethyl groups, such as -bis (trichloromethyl) -s-triazine, are included.

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

The said triazine type compound can be used individually or in combination of 2 or more types.

When using a triazine-based compound as the photopolymerization initiator, the amount of the triazine-based compound is preferably 0.01 to 40 parts by weight, more preferably 1 to 30, based on 100 parts by weight of the total weight of the (C) polyfunctional and monofunctional monomers. Parts by weight, particularly preferably 1 to 20 parts by weight.

When the amount of the triazine-based compound is less than 0.01 part by weight, it may be difficult to obtain a pixel array arranged in a predetermined pattern due to insufficient curing due to exposure, and when the amount exceeds 40 parts by weight, the formed colored layer is developed during development. It can be easily removed from the substrate.

additive

Various additives can be added arbitrarily to the radiation sensitive composition for color filters of this invention.

Examples of the additives include extender pigments such as barium sulfate or calcium carbonate; Dispersion aids such as derivatives of blue pigments such as copper phthalocyanine derivatives or derivatives of yellow pigments; Fillers such as glass or alumina; Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or poly (fluoroalkylacrylate); Nonionic, cationic or anionic surfactants; Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxyoxytrimethylsilane, 3-glycidoxyoxymethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane ; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) or 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole or alkoxybenzophenone; And anti-agglomerating agents such as sodium polyacrylate.

(B) When alkali-soluble resin has a carboxyl group, in order to improve the solubility to the alkali developing solution of the coating film formed from the radiation sensitive composition for color filters of this invention, and to further suppress the remainder of a cosmetic product after image development, An organic acid can be further added to the. The organic acid is preferably aliphatic carboxylic acid or phenyl group-containing carboxylic acid.

Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasilic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; And tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid.

The phenyl group-containing carboxylic acid is, for example, an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group or a carboxylic acid in which a carboxyl group is bonded to a phenyl group through a carbon chain.

Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylic acid; Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Aromatic polycarboxylic acids having three or more carboxyl groups such as trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamic acid, kumaric acid and umbelic acid.

Among these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and phthalic acid are alkali-soluble, solubility in the solvents detailed below, And from the viewpoint of preventing smudges or film residues in regions other than the portions forming the pixels.

The said organic acid can be used individually or in combination of 2 or more types.

The amount of the organic acid in the present invention is preferably 10% by weight or less, more preferably 0.001 to 10% by weight, still more preferably 0.01 to 1% by weight based on the total amount of the radiation-sensitive composition. When the amount of the organic acid exceeds 10% by weight, the adhesion of the formed pixel to the substrate may decrease.

Particularly preferred examples (1) to (4) of the radiation sensitive composition for color filters of the present invention are as follows.

(1) (B) Alkali-soluble resin is a copolymer of Nm-hydroxyphenylmaleimide, (meth) acrylic acid, styrene and benzyl (meth) acrylate, Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene and Copolymers of benzyl (meth) acrylate, No-hydroxyphenylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, copolymers of styrene and benzyl (meth) acrylate, Np -Hydroxyphenylmaleimide, (meth) acrylic acid, copolymer of 2- (meth) acryloyloxyethylsuccinic acid, styrene and benzyl (meth) acrylate, Np-hydroxyphenylmaleimide, (meth) acrylic acid, ω Carboxypolycaprolactone mono (meth) acrylates, copolymers of styrene and benzyl (meth) acrylates, and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, benzyl (meth) acrylates and glycerol mono (Met) At least one alkali-soluble resin (B3) selected from the group consisting of copolymers of acrylates, wherein (D) the photopolymerization initiator is selected from the group consisting of acetophenone compounds, biimidazole compounds, and triazine compounds The radiation sensitive composition for color filters containing 1 or more types.

(2) (B) at least one unsaturated compound (N- (monohydroxy) in which the alkali-soluble resin is selected from the group consisting of N-substituted maleimide, N-substituted (meth) acrylate and (meth) acrylic acid ester Phenyl) maleimide), (2) (meth) acrylic acid, or 1 selected from the group consisting of ω-carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethylsuccinic acid Combination of at least one other carboxyl group-containing ethylenically unsaturated monomer with (meth) acrylic acid, (3) styrene and (4) methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) At least one (meth) selected from the group consisting of acrylates, phenyl (meth) acrylates, glycerol mono (meth) acrylates, polystyrene macromonomers and polymethyl methacrylate macromonomers (B1) Alkali-soluble resin which is a copolymer of acrylic acid ester, (D) For a color filter containing a photoinitiator containing 1 or more types chosen from the group which consists of an acetophenone type compound, a biimidazole type compound, and a triazine type compound. Radiation-sensitive composition.

(3) The radiation sensitive composition for color filters whose polyfunctional monomer is 1 or more types chosen from the group which consists of a trimethylol propane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate (1) Or (2).

(4) The radiation sensitive composition (1) to (3) for color filters, in which the colorant (A) contains an organic pigment.

menstruum

The radiation sensitive composition for color filters of this invention contains the said (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator as an essential component, and may optionally contain the said additive. Can be. The radiation sensitive composition is advantageously prepared as a liquid composition in which these components are dispersed or dissolved in a suitable solvent.

It is possible to select and use a suitable solvent which disperses or dissolves each component constituting the composition and does not react with such components and has suitable volatility.

Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Cypionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl- 3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl Other such as butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutyrate Termini's like; Aromatic hydrocarbons such as toluene and xylene; And carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

These solvents may be used alone or in combination of two or more thereof.

In addition, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, di High boiling point solvents such as ethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate can be used in combination with the solvent.

These high boiling point solvents can be used individually or in combination of 2 or more types.

In view of the solubility, pigment dispersibility and coating properties in the solvent, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxy Preferred are propionate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate . Among the above high boiling point solvents, gamma -butyrolactone is preferable.

The amount of the solvent in the present invention is preferably 100 to 10,000 parts by weight, more preferably 500 to 5,000 parts by weight based on 100 parts by weight of the (B) alkali-soluble resin.

Manufacturing method of color filter

The method of manufacturing a color filter using the radiation sensitive composition for color filters of this invention is demonstrated next.

First, a light shielding layer is formed to determine a portion for forming a pixel on the surface of the substrate, and then a liquid radiation-sensitive composition in which red pigment is dispersed is applied onto the substrate, and then pre-fired to evaporate the solvent to form a coating film. do. Thereafter, the coating film is exposed to radiation through a photo mask and developed with an alkaline developer to dissolve and remove the non-exposed portions of the coating film to form a pixel array in which red pixels are arranged in a predetermined pattern.

Thereafter, as described above with a liquid radiation-sensitive composition in which green or blue pigments are dispersed and prebaked, and then exposed to radiation and developed, a green pixel array and a blue pixel array are sequentially formed on the same substrate. The color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. The order of forming the pixel array in manufacturing the color filter is, of course, not limited to the above order.

Substrates used in the production of color filters are made of glass, silicon, polycarbonates, polyesters, aromatic polyamides, polyamide imides or polyimides. Optionally, the substrate may be subjected to appropriate pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, vapor phase-reaction or vacuum deposition with a silane coupling agent.

Appropriate coating techniques such as spin coating, cast coating or roll coating can be used to apply the liquid composition.

The thickness of the coating film after drying is preferably 0.1 to 10 mu m, more preferably 0.2 to 5.0 mu m, particularly preferably 0.2 to 3.0 mu m.

The radiation used for the production of the color filter can be selected from visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray, and preferably has a wavelength of 190 to 450 nm.

The amount of energy of the radiation is preferably 10 to 10,000 J / m 2.

The alkaline developer is sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene or 1,5-diazabicyclo- [4.3.0 ] Aqueous solutions, such as] -5-nonene, are preferable.

A proper amount of water-soluble organic solvent or surfactant such as methanol or ethanol can be added to the alkaline developer. It is preferable to wash | clean a coating film after image development with alkaline developing solution.

The developing method may be a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method, or the like. It is preferable to develop for 5 to 300 second at normal temperature as image development conditions.

When the shower developing method is performed at a temperature of 23 ° C. and a developing pressure of 1 kgf / cm 2 (nozzle diameter 1 mm), the dissolution time of the unexposed portion is more than 20 seconds for the radiation sensitive composition for a conventional color filter. As will be apparent from the examples described below, in the case of the radiation sensitive composition for color filters of the present invention, the time is 20 seconds or less.

The color filter thus produced is very useful, for example, in color liquid crystal display devices, color image tube elements, color sensors, and the like.

The radiation sensitive composition for color filters of the present invention can shorten the tact time without generating residues or stains on the substrate and the light shielding layer of the unexposed portion at the time of development, and the alkali solubility is significantly improved, resulting in high definition and high efficiency. High quality pixels can be formed.

Therefore, the radiation sensitive composition for color filters of this invention can be used very advantageously for manufacture of the color filter containing the color filter for color liquid crystal display devices, and the color filter for color separation of a solid-state image sensor.

Example

Comparative Example 1

(A) As a coloring agent, C.I. Pigment Green 36, C.I. Pigment Yellow 150 and C.I. 100 parts by weight of a mixture of pigment yellow 138 (weight ratio = 50/35/15), 10 parts by weight of BYK-2001 as a dispersant, (B) N-phenylmaleimide, methacrylic acid, styrene and benzyl methacryl as alkali-soluble resins 50 parts by weight of copolymer of the rate (weight ratio = 30/20/20/30), (C) 40 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D) 2-benzyl-2-dimethyl as the photopolymerization initiator A liquid radiation-sensitive composition was prepared by mixing 30 parts by weight of amino-1- (4-morpholinophenyl) butan-1-one and 1,500 parts by weight of ethyl 3-ethoxypropionate as a solvent.

This liquid radiation-sensitive composition was applied using a spin coater on the surface of a sodium glass substrate having a SiO ₂ film formed thereon to prevent elution of sodium ions, and then prebaked at 90 ° C. for 4 minutes to have a thickness of 1.3 μm. Phosphorus coated film was formed. Thereafter, the substrate was cooled to room temperature, and ultraviolet light having a wavelength of 365 nm was exposed at 2,000 J / m 2 through the photo mask through the photomask through the photomask. A 0.04% by weight aqueous potassium hydroxide solution was sprayed onto the exposed coated film at a developing pressure of 1 kgf / cm 2 (nozzle diameter 1 mm) at 23 ° C. for the shower developing method.

As a result, the time required for complete dissolution of the unexposed part was 25 seconds.

Example 1

Np-hydroxyphenylmaleimide, methacrylic acid, styrene and benzyl methacrylate as (B3) alkali-soluble resin in place of 50 parts by weight of (B) alkali-soluble resin in Comparative Example 1 (weight ratio = 30/20/20 A liquid radiation sensitive composition was prepared in the same manner as in Comparative Example 1, except that 50 parts by weight of the copolymer of / 30) was used.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 19 seconds.

Example 2

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 80 parts by weight of a mixture of Pigment Red 177 (weight ratio = 90/10), 8 parts by weight of BYK-165 as a dispersant, (B1) Np-hydroxyphenyl methacrylamide, methacrylic acid, styrene and benzyl meta as alkali-soluble resin 40 parts by weight of a copolymer of acrylate (weight ratio = 35/20/20/25), (C) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-benzyl-2- as photopolymerization initiator A liquid radiation-sensitive composition was prepared by mixing 30 parts by weight of dimethylamino-1- (4-morpholinophenyl) butan-1-one and 1,300 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 17 seconds.

Example 3

(A) As a coloring agent, C.I. Pigment Blue 15: 6 and C.I. 90 parts by weight of a mixture of pigment violet 23 (weight ratio = 95/5), 15 parts by weight of BYK-2001 as a dispersant, (B1) Np-hydroxyphenyl methacrylate, methacrylic acid, styrene, benzyl meta as alkali-soluble resin 50 parts by weight of a copolymer of acrylate and glycerol methacrylate (weight ratio = 25/20/20/20/15), (C) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) a photopolymerization initiator 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 1,500 parts by weight of propylene glycol monomethyl ether acetate as a solvent were prepared to prepare a liquid radiation-sensitive composition. .

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 15 seconds.

Example 4

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 100 parts by weight of a mixture of Pigment Yellow 150 (weight ratio = 50/50), 15 parts by weight of BYK-170 as a dispersant, (B1) Np-carboxyphenylmaleimide, methacrylic acid, 2-methacryloyl as an alkali-soluble resin 50 parts by weight of a copolymer of oxyethylsuccinic acid, styrene and benzyl methacrylate (weight ratio = 30/20/10/20/20), (C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D ) Liquid radiation by mixing 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator and 1,200 parts by weight of ethyl 3-ethoxypropionate as a solvent The sexual composition was prepared.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 12 seconds.

Example 5

(A) As a coloring agent, C.I. Pigment Blue 15: 6 100 parts by weight, 15 parts by weight of BYK-2000 as a dispersant, (B1) N-2,6-dimethyl-4-hydroxyphenylmaleimide, methacrylic acid, styrene and benzyl meta as alkali-soluble resins 50 parts by weight of a copolymer of acrylate (weight ratio = 35/20/25/20), (C) 70 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-methyl-1- as a photopolymerization initiator 30 parts by weight of a mixture of (4-methylthiophenyl) -2-morpholinopropane-1-one and 4,4'-bis (diethylamino) benzophenone (weight ratio = 20/10) and ethyl 3- as solvent A liquid radiation-sensitive composition was prepared by mixing a mixture of 700 parts by weight of ethoxypropionate and 700 parts by weight of propylene glycol monomethyl ether.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 19 seconds.

Example 6

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 90 parts by weight of a mixture of Pigment Yellow 139 (weight ratio = 80/20), 20 parts by weight of EFKA-47 as a dispersant, (B1) N- (3,5-dimethyl-4-hydroxyphenyl) maleimide as an alkali-soluble resin , 50 parts by weight of a copolymer of methacrylic acid, styrene, benzyl methacrylate and glycerol methacrylate (weight ratio = 30/20/15/20/15), (C) dipentaerythritol hexaacrylate as a polyfunctional monomer 70 parts by weight, (D) 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator and 1,500 parts by weight of propylene glycol monomethyl ether acetate as a solvent To prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 17 seconds.

Example 7

(A) As a coloring agent, C.I. Pigment Green 36, C.I. Pigment Yellow 150 and C.I. 110 parts by weight of a mixture of pigment yellow 138 (weight ratio = 70/15/15), 15 parts by weight of BYK-161 as a dispersant, (B1) Np-hydroxycyclohexylmaleimide, methacrylic acid, ω- as alkali-soluble resin Carboxypolycaprolactone monomethacrylate, 60 parts by weight of copolymer of styrene and benzyl methacrylate (weight ratio = 30/20/10/20/20), (C) dipentaerythritol hexaacrylate as polyfunctional monomer 70 parts by weight, (D) 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator and 1,500 parts by weight of propylene glycol monomethyl ether acetate as a solvent To prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 19 seconds.

Example 8

(A) As a coloring agent, C.I. Pigment Green 36, C.I. Pigment Yellow 150 and C.I. 110 parts by weight of a mixture of Pigment Yellow 138 (weight ratio = 70/15/15), 15 parts by weight of BYK-161 as a dispersant, (B1) Np-carboxycyclohexylmaleimide, methacrylic acid, styrene and benzyl as alkali-soluble resins 60 parts by weight of copolymer of methacrylate (weight ratio = 35/20/25/20), (C) 60 parts by weight of dipentaerythritol hexaacrylate as polyfunctional monomer, (D) 2-benzyl-2 as photopolymerization initiator 30 parts by weight of -dimethylamino-1- (4-morpholinophenyl) butan-1-one and 1,500 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 11 seconds.

Example 9

(A) As a coloring agent, C.I. Pigment Red 224, C.I. Pigment Red 177 and C.I. 80 parts by weight of a mixture of Pigment Yellow 139 (weight ratio = 45/35/20), 10 parts by weight of BYK-2001 as a dispersant, (B3) No-hydroxyphenylmaleimide, methacrylic acid, ω-carboxy as an alkali-soluble resin 60 parts by weight of polycaprolactone monomethacrylate, a copolymer of styrene and benzyl methacrylate (weight ratio 25/20/10/25/20), (C) dipentaerythritol hexaacrylate 60 as a polyfunctional monomer Parts by weight, (D) 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator, and 1,500 parts by weight of propylene glycol monomethyl ether acetate as a solvent A liquid radiation sensitive composition was prepared.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 14 seconds.

Example 10

(A) As a coloring agent, C.I. Pigment Red 224, C.I. Pigment Red 177 and C.I. 80 parts by weight of a mixture of pigment yellow 139 (weight ratio = 45/35/20), 10 parts by weight of BYK-2001 as a dispersant, (B3) Nm-hydroxyphenylmaleimide, methacrylic acid, styrene and benzyl as alkali-soluble resins 50 parts by weight of copolymer of methacrylate (weight ratio = 35/20/25/20), (C) 60 parts by weight of dipentaerythritol hexaacrylate as polyfunctional monomer, (D) 2-benzyl-2 as photopolymerization initiator 30 parts by weight of -dimethylamino-1- (4-morpholinophenyl) butan-1-one and 1,500 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 18 seconds.

Example 11

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 100 parts by weight of a mixture of Pigment Red 177 (weight ratio = 80/20), 30 parts by weight of BYK-2001 as a dispersant, (B3) Np-hydroxyphenylmaleimide, methacrylic acid, styrene and benzyl methacryl as alkali-soluble resins 80 parts by weight of the copolymer of the rate (weight ratio = 30/20/20/30), (C) 70 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D) 2-benzyl-2-dimethyl as the photopolymerization initiator 30 parts by weight of amino-1- (4-morpholinophenyl) butan-1-one, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1 2 parts by weight of 2'-biimidazole, 2 parts by weight of 4,4'-bis (diethylamino) benzophenone and 1 part by weight of 2-mercaptobenzothiazole and ethyl 3-ethoxypropionate as solvent A liquid radiation-sensitive composition was prepared by mixing a mixture of 600 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 18 seconds.

Example 12

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 120 parts by weight of a mixture of Pigment Yellow 150 (weight ratio = 50/50), 30 parts by weight of BYK-2001 as a dispersant, (B3) Np-hydroxyphenylmaleimide, methacrylic acid, styrene and benzyl methacryl as alkali-soluble resins 70 parts by weight of the copolymer of the rate (weight ratio = 30/20/20/30), (C) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D) 2-benzyl-2-dimethyl as the photopolymerization initiator 35 parts by weight of amino-1- (4-morpholinophenyl) butan-1-one, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1 2 parts by weight of 2'-biimidazole, 2 parts by weight of 4,4'-bis (diethylamino) benzophenone and 1 part by weight of 2-mercaptobenzothiazole and 540 parts by weight of 3-methoxybutyl acetate And a mixture of 360 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 19 seconds.

Example 13

(A) As a coloring agent, C.I. Pigment Blue 15: 6 and C.I. 90 parts by weight of a mixture of pigment violet 23 (weight ratio = 95/5), 25 parts by weight of BYK-2001 as a dispersant, (B3) Np-hydroxyphenylmaleimide, methacrylic acid, styrene and benzyl methacryl as alkali-soluble resins 60 parts by weight of the copolymer of the rate (weight ratio = 30/20/20/30), (C) 90 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D) 2-methyl-1- (as the photopolymerization initiator 30 parts by weight of 4-methylthiophenyl) -2-morpholinopropane-1-one, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1 2 parts by weight of 2,2'-biimidazole, 6 parts by weight of 4,4'-bis (diethylamino) benzophenone and 2 parts by weight of 2-mercaptobenzothiazole and 540 parts by weight of 3-methoxybutyl acetate And a mixture of 360 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 16 seconds.

Example 14

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 110 parts by weight of a mixture of Pigment Yellow 139 (weight ratio = 85/15), 30 parts by weight of BYK-2001 as a dispersant, (B1) Np-hydroxyphenyl methacrylamide, methacrylic acid, styrene and benzyl meta as alkali-soluble resin 75 parts by weight of a copolymer of acrylate (weight ratio = 35/20/20/25), (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-benzyl-2- as photopolymerization initiator Dimethylamino-1- (4-morpholinophenyl) butan-1-one 30 parts by weight, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl- 3 parts by weight of 1,2'-biimidazole, 4 parts by weight of 4,4'-bis (diethylamino) benzophenone and 2 parts by weight of 2-mercaptobenzothiazole and ethyl 3-ethoxypropio as a solvent A liquid radiation-sensitive composition was prepared by mixing a mixture of 550 parts by weight of nate and 550 parts by weight of propylene glycol monomethyl ether acetate.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 15 seconds.

Example 15

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 120 parts by weight of a mixture of Pigment Yellow 138 (weight ratio = 50/50), 30 parts by weight of BYK-2001 as a dispersant, (B1) Np-hydroxyphenyl methacrylamide, methacrylic acid, styrene and benzyl meta as alkali-soluble resin 70 parts by weight of a copolymer of acrylate (weight ratio = 35/20/20/25), (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-benzyl-2- as photopolymerization initiator Dimethylamino-1- (4-morpholinophenyl) butan-1-one 35 parts by weight, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl- 3-methoxybutyl acetate 400 as a mixture and solvent of 3 parts by weight of 1,2'-biimidazole, 3 parts by weight of 4,4'-bis (diethylamino) benzophenone and 2 parts by weight of 2-mercaptobenzothiazole A liquid radiation-sensitive composition was prepared by mixing a mixture of parts by weight and 600 parts by weight of propylene glycol monomethyl ether acetate.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 17 seconds.

Example 16

(A) As a coloring agent, C.I. Pigment Blue 15: 6 80 parts by weight, 25 parts by weight of BYK-2001 as a dispersant, (B1) Np-hydroxyphenyl methacrylamide, methacrylic acid, styrene and benzyl methacrylate as the alkali-soluble resin (weight ratio = 35 / 60 parts by weight of the copolymer of 20/20/25), (C) 90 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, and (D) 2-methyl-1- (4-methylthiophenyl) as the photopolymerization initiator 20 parts by weight of -2-morpholinopropane-1-one, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimi 3 parts by weight of dazole, 6 parts by weight of 4,4'-bis (diethylamino) benzophenone and 1 part by weight of 2-mercaptobenzothiazole and 450 parts by weight of ethyl 3-ethoxypropionate and propylene glycol as a solvent A mixture of 450 parts by weight of monomethyl ether acetate was mixed to prepare a liquid radiation-sensitive composition.

This liquid composition was applied, prebaked, exposed and developed in the same manner as in Comparative Example 1.

As a result, the time required for complete dissolution of the unexposed part was 14 seconds.

The radiation sensitive composition for color filters according to the present invention is excellent in alkali developability, and does not generate residues or stains on the substrate and the light shielding layer of the unexposed part during development, and can significantly shorten the tact time.

Claims (9)

(A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, Comprising: (B) alkali-soluble resin (B1) (1) copolymerizable with at least one unsaturated compound selected from the group consisting of N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester, and (2) unsaturated compounds As a copolymer of another ethylenically unsaturated monomer, the N-substituted maleimide is a phenyl group substituted with a hydrogen atom in the imide group of the maleimide by (a1) a hydroxyl group, a carboxyl group, or both, or (a2) a hydroxide. A compound obtained by substituting a cyclohexyl group substituted by a hydroxyl group, a carboxyl group, or both (excluding N- (monohydroxyphenyl) maleimide), and the N-substituted (meth) acrylamide is (meth A cyclohexyl substituted with one hydrogen atom in the amide group of acrylamide by (b1) a phenyl group substituted by a hydroxyl group, a carboxyl group, or both, or (b2) a hydroxyl group, a carboxyl group, or both. Wherein the (meth) acrylic acid ester is a phenyl group substituted with a hydrogen atom in the carboxyl group of (meth) acrylic acid by a (c1) hydroxyl group, a carboxyl group, or both, or (c2) a hydroxyl group, A copolymer which is a compound obtained by substituting a cyclohexyl group substituted by a carboxyl group or both; (B2) 1 selected from the group consisting of (1) N- (monohydroxyphenyl) maleimide, (2) said N-substituted maleimide, N-substituted (meth) acrylamide and (meth) acrylic acid ester At least one unsaturated compound (excluding N- (monohydroxyphenyl) maleimide), and (3) a copolymer of said other ethylenically unsaturated monomer; And (B3) (1) N- (monohydroxyphenyl) maleimide, (2) (meth) acrylic acid, (3) styrene and (4) methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , Benzyl (meth) acrylates, phenyl (meth) acrylates, glycerol mono (meth) acrylates, macromonomers with mono (meth) acryloyl groups at the ends of the polymer molecular chains of polystyrene and polymethyl (meth) acrylates Copolymer of at least one (meth) acrylic acid ester selected from the group consisting of macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain of The radiation sensitive composition for color filters characterized by the above-mentioned. The radiation sensitive composition for color filters of Claim 1 whose content of (B) alkali-soluble resin is 10-1,000 weight part based on 100 weight part of (A) coloring agents. The radiation sensitive composition for color filters of Claim 1 whose content of (C) polyfunctional monomer is 5-500 weight part based on 100 weight part of (B) alkali-soluble resin. The radiation sensitive composition for color filters of Claim 1 whose amount of (D) photoinitiator is 0.01-80 weight part based on 100 weight part of (C) polyfunctional monomers. (B) Alkali-soluble resin is a copolymer of Nm-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, and benzyl (meth) acrylate, Np-hydroxyphenylmaleimide, (meth) acrylic acid , Copolymers of styrene and benzyl (meth) acrylate, No-hydroxyphenylmaleimide, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, styrene and benzyl (meth) acrylate Copolymer, Np-hydroxyphenylmaleimide, (meth) acrylic acid, copolymer of 2- (meth) acryloyloxyethylsuccinic acid, styrene and benzyl (meth) acrylate, Np-hydroxyphenylmaleimide, (meth) Copolymers of acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, styrene and benzyl (meth) acrylate, and Np-hydroxyphenylmaleimide, (meth) acrylic acid, styrene, benzyl (meth) acrylate And glycerol At least one (B3) copolymer selected from the group consisting of a copolymer of mono (meth) acrylate, and (D) the photopolymerization initiator is selected from the group consisting of an acetophenone compound, a biimidazole compound, and a triazine compound The radiation sensitive composition for color filters which are 1 or more types. The method of claim 1, wherein (B) alkali-soluble resin is (meth) acrylic acid and ω-carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl succinic acid as component (2). (B1) is a copolymer comprising a combination with at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of (D) a photoinitiator is an acetophenone compound, a biimidazole compound, and a triazine compound. The radiation sensitive composition for color filters selected from the group consisting of. The radiation sensitive composition for color filters according to claim 1, wherein (C) the polyfunctional monomer is at least one member selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. . The radiation sensitive composition for color filters of Claim 1 in which (A) the coloring agent contains an organic pigment. A color filter obtained by exposing the composition of claim 1 to radiation.