KR20070114649A - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Abstract

A radiation-sensitive composition for forming a colored layer is provided to ensure excellent shelf stability as a liquid composition while maintaining good sensitivity, resolution and pattern shape, and to form a pattern having excellent solvent resistance and adhesion to a substrate. A radiation-sensitive composition for forming a colored layer comprises: (A) a colorant; (B) an alkali soluble resin; (C) a multi-functional monomer; and (D) a photopolymerization initiator. The alkali soluble resin(B) comprises a copolymer of: (b1) at least one first unsaturated compound selected from the group consisting of an unsaturated carboxylic acids, unsaturated carboxylic anhydrides and unsaturated phenolic compounds; and at least one second unsaturated compound selected from (b2) an unsaturated compound containing an oxetane backbone, and (b3) an unsaturated compound having a tetrahydrofuran backbone.

Description

Radiation-sensitive composition, color filter and color liquid crystal display element for colored layer formation {RADIATION SENSITIVE COMPOSITION FOR FORMING A COLORED LAYER, COLOR FILTER AND COLOR LIQUID CRYSTAL DISPLAY DEVICE}

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Application Laid-Open No. 3-53201

The present invention relates to a radiation sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device. More specifically, the radiation sensitive composition used for formation of the colored layer useful for the color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, etc., and the colored layer formed using the said radiation sensitive composition are provided. It relates to a color filter, and a color liquid crystal display device comprising the color filter.

Conventionally, in manufacturing a color filter using a colored radiation-sensitive composition, after applying a colored radiation-sensitive composition on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance, the dried coating film is formed into a desired pattern shape. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as "exposure") and developing it (see Japanese Patent Laid-Open No. Hei 2-144502 and Japanese Patent Laid-Open No. Hei 3-53201). Known.

In recent years, in the field of color filter technology, the performance requirements for formed pixels, black matrices, and colored radiation-sensitive compositions become increasingly stringent, and in addition to the sensitivity, resolution, pattern shape, and the like as colored radiation-sensitive compositions, pixels and black matrices There is a strong demand for excellent solvent resistance to a wide range of solvents and good adhesion to a substrate, and from the viewpoint of production control of color filters, the colored radiation-sensitive composition used for the formation of color filters is a storage stability as a liquid composition containing a solvent. Although this excellent viscosity is strongly demanded, such a request could not be sufficiently satisfied with the conventional colored radiation-sensitive composition.

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel radiation-sensitive composition for forming a colored layer, which provides a pixel and a black matrix having good storage stability as a liquid composition containing a solvent, excellent solvent resistance to a wide range of solvents, and adhesion to a substrate. To provide.

Another object of the present invention is to provide a color filter and a color liquid crystal display device.

Still 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 are, firstly,

(A) A radiation sensitive composition containing a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (B) alkali-soluble resin is (b1) unsaturated carboxylic acid, unsaturated At least one first unsaturated compound selected from the group consisting of carboxylic anhydrides and unsaturated phenol compounds, (b2) unsaturated compounds having an oxetane skeleton, and (b3) unsaturated compounds having a tetrahydrofuran skeleton A radiation sensitive composition comprising a copolymer of at least one second unsaturated compound, wherein the radiation sensitive composition is used to form a colored layer.

In the present invention, the colored layer means "pixel and / or black matrix".

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

It is achieved by the color filter which comprises the colored layer formed using the radiation sensitive composition of this invention.

In addition, according to the present invention, the above objects and advantages of the present invention are third,

It is achieved by the color liquid crystal display device provided with the color filter of the present invention.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Radiation  Composition

-(A) colorant-

 The coloring agent in this invention is not specifically limited in color tone, According to the use of the color filter obtained, it is suitably selected, It can be any of a pigment, dye, or a natural pigment.

Since the color filter requires high color development and heat resistance, as the colorant in the present invention, a colorant having high color resistance and high heat resistance, particularly a colorant having high thermal decomposition resistance, is preferably used, and organic pigments or inorganic pigments are usually used, particularly preferably. The organic pigment, carbon black is used.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), specifically, The same color index (CI) number is attached | subjected.

C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, 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 60, C.I. Pigment Yellow 61, C.I. Pigment Yellow 65, C.I. Pigment Yellow 71, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 100, C.I. Pigment Yellow 101, C.I. Pigment Yellow 104, C.I. Pigment Yellow 106, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 116, C.I. Pigment Yellow 117, C.I. Pigment Yellow 119, C.I. Pigment Yellow 120, C.I. Pigment Yellow 126, C.I. Pigment Yellow 127, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 175, C.I. Pigment Yellow 180, C.I. Pigment yellow 185;

C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment orange 73;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 37, C.I. Pigment Red 38, C.I. Pigment Red 40, C.I. Pigment Red 41, C.I. Pigment Red 42, C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 50: 1, C.I. Pigment Red 52: 1, C.I. Pigment Red 53: 1, C.I. Pigment Red 57, C.I. Pigment Red 57: 1, C.I. Pigment Red 57: 2, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 64: 1, C.I. Pigment Red 81: 1, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 90: 1, C.I. Pigment Red 97,

C.I. Pigment Red 101, C.I. Pigment Red 102, C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108, C.I. Pigment Red 112, C.I. Pigment Red 113, C.I. Pigment Red 114, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 151, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 172, C.I. Pigment Red 174, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 188, C.I. Pigment Red 190, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment red 265;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment blue 60;

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

C.I. Pigment Brown 23, C.I. Pigment brown 25;

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

These organic pigments can be used, for example, by refining by sulfuric acid recrystallization, solvent washing, or a combination thereof.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, red ocher (red iron oxide (III)), cadmium, ultramarine blue, blue blue, and chromium oxide. Rust, cobalt rust, amber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

In the present invention, the organic pigment and the inorganic pigment may be used alone or in combination of two or more thereof. Moreover, an organic pigment and an inorganic pigment can be used together. When forming a pixel, preferably at least one organic pigment is used, and when forming a black matrix, preferably at least two organic pigments and / or carbon black are used.

In the present invention, each of the pigments may be used by modifying the particle surface thereof with a polymer if desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., the polymer for various pigment dispersions, or oligomer etc. are mentioned, for example.

In addition, in the present invention, the colorant may be used together with a dispersant if desired.

As said dispersing agent, surfactant, such as a cationic type, an anionic type, nonionic type, amphoteric, silicone type, and fluorine type, is mentioned, for example.

As said surfactant, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-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; In addition to polyethyleneimine and the like, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and Mega Pack (trade name) Dainippon Ink & Chemicals Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), BYK, Disperbyk (above) And Big Chemi Japan Co., Ltd., Sol Spas (Seneka Co., Ltd.), etc. are mentioned.

These surfactant can be used individually or in mixture of 2 or more types.

The amount of the surfactant to be used is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight with respect to 100 parts by weight of the colorant.

In this invention, a radiation sensitive resin composition can be manufactured by a suitable method, for example, can be manufactured by mixing (A)-(D) component with a solvent and the additive mentioned later as needed. In the case of using a pigment as a colorant, the pigment is mixed and dispersed in the solvent in the presence of a dispersant, optionally with a part of component (B), for example, by grinding using a bead mill, a roll mill, or the like to obtain a pigment dispersion. And it is preferable to manufacture this by adding and mixing (B)-(D) component with an additional solvent and additive as needed.

The amount of the dispersant used in preparing the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, particularly preferably 10 based on 100 parts by weight of the pigment. To 50 parts by weight. When the usage-amount of a dispersing agent exceeds 100 weight part, there exists a possibility that developability etc. may be impaired.

Moreover, as a solvent used when manufacturing a pigment dispersion liquid, the same thing as the solvent illustrated about the liquid composition of the radiation sensitive resin composition mentioned later is mentioned, for example.

The amount of the solvent used when preparing the pigment dispersion is preferably 500 to 1,000 parts by weight, more preferably 700 to 900 parts by weight based on 100 parts by weight of the pigment.

In the production of the pigment dispersion, when producing using a bead mill, a pigment mixture containing a pigment, a solvent, and a dispersant is preferably used, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm. It can carry out by mixing and dispersing, cooling with cooling water or the like.

In this case, the filling rate of the beads is preferably 50 to 80% of the mill capacity, and the injection amount of the pigment mixed liquid is preferably about 20 to 50% of the mill capacity. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

In addition, when manufacturing using a roll mill, it can carry out by processing, for example, using a triaxial roll mill, a biaxial roll mill, etc., cooling a pigment mixture liquid with cooling water etc. preferably.

In this case, it is preferable that a roll space | interval is 10 micrometers or less, and a shear force becomes like this. Preferably it is about 10 ⁸ dyn / sec. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

-(B) alkali-soluble resin-

Alkali-soluble resin in this invention is a case where (b1) 1 or more 1st unsaturated compound selected from the group which consists of unsaturated carboxylic acid, unsaturated carboxylic anhydride, and unsaturated phenol compound (henceforth "acidic unsaturated compound") And (b) a copolymer of at least one second unsaturated compound selected from the group consisting of an unsaturated compound having an oxetane skeleton and (b3) an unsaturated compound having a tetrahydrofuran skeleton, and (A) a colorant. It is a component which has solubility with respect to the alkaline developing solution used at the image development process process at the time of forming a colored layer, acting as a binder with respect to.

As alkali-soluble resin (B), More specifically, the copolymer of (B1) acidic unsaturated compound, the unsaturated compound which has an oxetane skeleton (henceforth "oxetane unsaturated compound"), (B2) acidic unsaturated compound, Copolymers of unsaturated compounds having a tetrahydrofuran skeleton (hereinafter referred to as "tetrahydrofuran unsaturated compounds"), and (B3) acidic unsaturated compounds with copolymers of oxetane unsaturated compounds and tetrahydrofuran unsaturated compounds. have.

In the copolymers (B1), (B2) and (B3), examples of the unsaturated carboxylic acid or acid anhydride thereof in the acidic unsaturated compound include

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid;

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acid, such as monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate.

Among these unsaturated carboxylic acids or acid anhydrides thereof, monosuccinate (2-acryloyloxyethyl) and monophthalic acid (2-acryloyloxyethyl) are each represented by light ester HOA-MS and light ester HOA-MPE (above, It is marketed under the brand name of Kyoeisha Chemical Co., Ltd.).

Moreover, as an unsaturated phenol compound in an acidic unsaturated compound, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, 2-methyl-4- vinyl phenol, 3-methyl-4- vinyl phenol, o-iso, for example. Unsaturated phenols such as propenylphenol, m-isopropenylphenol and p-isopropenylphenol;

2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1- Unsaturated naphthol, such as naphthol, etc. are mentioned.

In this invention, as an acidic unsaturated compound, (meth) acrylic acid, p-vinylphenol, etc. are preferable, and (meth) acrylic acid is especially preferable.

In the (B1) and (B3) copolymers, as the oxetane unsaturated compound, preferably, for example, a compound represented by the following general formula (1) (hereinafter referred to as "oxetane unsaturated compound (1)"), and the following general formula (2) The compound (henceforth "oxetane unsaturated compound (2)") etc. which are represented by these are mentioned.

In Formula 1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of one another A hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and n is an integer of 0 to 6;

[In the formula ^{2, R, R 1, R} 2, R 3, R 4, R 5 and n are each ^{R, R 1, R 2,} R 3, R 4, R 5 and n and consent of the formula (1) being]

In the formulas (1) and (2), examples of the alkyl group having 1 to 4 carbon atoms of R, R ¹ , R ² , R ³ , R ^4, and R ⁵ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, etc. are mentioned.

Moreover, as a C1-C4 fluoroalkyl group of R <^2> , R <^3> , R <^4> and R <^5> , it is a fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, 2-fluoro, for example. Roethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-i-propyl group, nonafluoro- n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group, etc. are mentioned.

Moreover, as a C6-C20 aryl group of R <^2> , R <^3> , R <^4> and R <^5> , a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, etc. are mentioned, for example.

As the oxetane unsaturated compound (1), for example, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -2-methyloxetane, 3-[( Meth) acryloyloxymethyl] -3-methyloxetane, 3-[(meth) acryloyloxymethyl] -2-ethyloxetane, 3-[(meth) acryloyloxymethyl] -3-ethyl Oxetane, 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) acryloyloxymethyl] -2-pentafluoroethyloxetane, 3- [ (Meth) acryloyloxymethyl] -2-phenyloxetane, 3-[(meth) acryloyloxymethyl] -2,2-difluorooxetane, 3-[(meth) acryloyloxymethyl ] -2,2,4-trifluorooxetane, 3-[(meth) acryloyloxymethyl] -2,2,4,4-tetrafluorooxetane,

3- [2- (meth) acryloyloxyethyl] oxetane, 3- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 3- [2- (meth) acryloyloxy Ethyl] -3-methyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -3-ethyloxetane , 3- [2- (meth) acryloyloxyethyl] -2-trifluoromethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyl oxetane, 3 -[2- (meth) acryloyloxyethyl] -2-phenyloxetane, 3- [2- (meth) acryloyloxyethyl] -2,2-difluorooxetane, 3- [2- (Meth) acryloyloxyethyl] -2,2,4-trifluorooxetane, 3- [2- (meth) acryloyloxyethyl] -2,2,4,4-tetrafluorooxetane (Meth) acrylic acid ester, such as these, etc. are mentioned.

As the oxetane unsaturated compound (2), for example, 2-[(meth) acryloyloxymethyl] oxetane, 2-[(meth) acryloyloxymethyl] -2-methyloxetane, 2- [(Meth) acryloyloxymethyl] -3-methyloxetane, 2-[(meth) acryloyloxymethyl] -4-methyloxetane, 2-[(meth) acryloyloxymethyl] -2 -Ethyl oxetane, 2-[(meth) acryloyloxymethyl] -3-ethyl oxetane, 2-[(meth) acryloyloxymethyl] -4-ethyl oxetane, 2-[(meth) acrylic Royloxymethyl] -2-trifluoromethyloxetane, 2-[(meth) acryloyloxymethyl] -3-trifluoromethyloxetane, 2-[(meth) acryloyloxymethyl]- 4-trifluoromethyloxetane, 2-[(meth) acryloyloxymethyl] -2-pentafluoroethyl oxetane, 2-[(meth) acryloyloxymethyl] -3-pentafluoroethyl Oxetane, 2-[(meth) acryloyloxymethyl] -4-pentafluoroethyl oxetane,

2-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] -3-phenyloxetane, 2-[(meth) acryloyloxymethyl] 4-phenyloxetane, 2-[(meth) acryloyloxymethyl] -2,3-difluorooxetane, 2-[(meth) acryloyloxymethyl] -2,4-difluoro Oxetane, 2-[(meth) acryloyloxymethyl] -3,3-difluorooxetane, 2-[(meth) acryloyloxymethyl] -3,4-difluorooxetane, 2 -[(Meth) acryloyloxymethyl] -4,4-difluorooxetane, 2-[(meth) acryloyloxymethyl] -3,3,4-trifluorooxetane, 2- [ (Meth) acryloyloxymethyl] -3,4,4-trifluorooxetane, 2-[(meth) acryloyloxymethyl] -3,3,4,4-tetrafluorooxetane,

2- [2- (meth) acryloyloxyethyl] oxetane, 2- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 2- [2- (meth) acryloyloxy Ethyl] -3-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -4-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane , 2- [2- (meth) acryloyloxyethyl] -3-ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -4-ethyloxetane, 2- [2- (meth ) Acryloyloxyethyl] -2-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-trifluoromethyloxetane, 2- [2- (meth) acrylic Royloxyethyl] -4-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyl oxetane, 2- [2- (meth) acryloyl Oxyethyl] -3-pentafluoroethyl oxetane, 2- [2- (meth) acryloyloxyethyl] -4-pentafluoroethyl oxetane,

2- [2- (meth) acryloyloxyethyl] -2-phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-phenyloxetane, 2- [2- (meth) Acryloyloxyethyl] -4-phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -2,3-difluorooxetane, 2- [2- (meth) acryloyloxy Ethyl] -2,4-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,3-difluorooxetane, 2- [2- (meth) acryloyloxy Ethyl] -3,4-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -4,4-difluorooxetane, 2- [2- (meth) acryloyloxy Ethyl] -3,3,4-trifluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,4,4-trifluorooxetane, 2- [2- (meth) (Meth) acrylic acid esters, such as acryloyloxyethyl] -3,3,4,4- tetrafluoro oxetane, etc. are mentioned.

Of these oxetane unsaturated compounds (1) and oxetane unsaturated compounds (2), 3-[(meth) cryloyloxymethyl] oxetane and 3-[(meth) cryloyloxymethyl] -3-ethyl ox Cetane, 3-[(meth) cryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) cryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryl Loyloxymethyl] oxetane, 2-[(meth) cryloyloxymethyl] -4-trifluoromethyloxetane, and the like are preferred, and 3- (methacryloyloxymethyl) oxetane, 3- (Methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyljade Cetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. have a wide development margin of the radiation-sensitive composition obtained and are also obtained. It is preferable at the point which improves the chemical resistance of a colored layer.

In the present invention, in addition to the oxetane unsaturated compound (1) and the oxetane unsaturated compound (2) as the oxetane unsaturated compound, for example, (3-oxetanylmethoxy) -p-vinylbenzene, Vinylphenols such as oxetanyl) ethoxy] -p-vinylbenzene, (2-oxetanylmethoxy) -p-vinylbenzene, and [2- (2-oxetanyl) ethoxy] -p-vinylbenzene (Oxetanylalkyl) ether;

(3-oxetanylmethyl) vinyl ether, [2- (3-oxetanyl) ethyl] vinyl ether, (2-oxetanylmethyl) vinyl ether, [2- (2-oxetanyl) ethyl] vinyl (Oxetanylalkyl) vinyl ethers, such as ether, etc. can also be used.

The said oxetane unsaturated compound can be used individually or in mixture of 2 or more types.

In the (B2) and (B3) copolymers, examples of the tetrahydrofuran unsaturated compound include tetrahydrofuran-2-yl (meth) acrylate and tetrahydrofuran-3-yl (meth) acrylate. Tetrahydrofuran esters of meth) acrylic acid;

Tetrahydrofurfuryl (meth) acrylate, 3-tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (3-tetrahydrofurfuryloxy) ethyl Tetrahydrofurfuryl group-containing esters of (meth) acrylic acid such as (meth) acrylate;

2- (meth) acryloyloxypropionate tetrahydrofurfuryl, 2- (meth) acryloyloxypropionic acid 3-tetrahydrofurfuryl, 2- (meth) acryloyloxypropionic acid 2- (tetrahydrofurfuryloxy Tetrahydrofurfuryl group-containing esters of 2- (meth) acryloyloxypropionic acid such as) ethyl and 2- (meth) acryloyloxypropionic acid 2- (3-tetrahydrofurfuryloxy) ethyl,

Vinylbenzene derivatives such as (tetrahydrofuran-2-yl) oxy-p-vinylbenzene, (tetrahydrofurfuryl) oxy-p-vinylbenzene and 2- (tetrahydrofurfuryloxy) ethoxy-p-vinylbenzene ;

And vinyl ethers such as (tetrahydrofuran-2-yl) vinyl ether, (tetrahydrofurfuryl) vinyl ether, and [2- (tetrahydrofurfuryloxy) ethyl] vinyl ether.

In the present invention, as the tetrahydrofuran unsaturated compound, a tetrahydrofurfuryl group-containing ester of (meth) acrylic acid is preferable, and in particular, tetrahydrofurfuryl (meth) acrylate and succinic acid [2- (meth) acryloyloxyethyl ] (Tetrahydrofurfuryl) is preferred.

The said tetrahydrofuran unsaturated compound can be used individually or in mixture of 2 or more types.

Copolymers (B1), (B2) and (B3) are optionally unsaturated compounds other than acidic unsaturated compounds, oxetane unsaturated compounds and tetrahydrofuran unsaturated compounds (hereinafter referred to as "other unsaturated compounds") as constituents. ) May be further contained.

As another unsaturated compound, for example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-methoxy styrene, p-meth Oxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Aromatic vinyl compounds such as;

Indenes such as indene and 1-methylindene;

Unsaturated imides such as maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, itaciconimide and citraconimide;

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, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxy propylene glycol (meth) acrylate, Toxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth Unsaturated carboxylic esters such as acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylic Unsaturated carboxylic acid aminoalkyl esters such as latex and 3-dimethylaminopropyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;

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;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene 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 compounds can be used individually or in mixture of 2 or more types.

In the present invention, the copolymer (B1) includes (b1) at least one acidic unsaturated compound having (meth) acrylic acid as an essential component, (b2) 3- (methacryloyloxymethyl) oxetane, and 3- ( Methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane , At least one oxetane unsaturated compound selected from the group consisting of 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and (B4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylic At least one polyvalent selected from the group consisting of latex, polystyrene macromonomers and polymethylmethacrylate macromonomers Copolymers containing other unsaturated compounds (hereinafter referred to as "copolymers (BI)") are preferred.

As a copolymer (BI), More specifically, for example

(b1) an acidic unsaturated compound comprising (meth) acrylic acid, and (b2) an oxetane unsaturated compound containing 3-[(meth) acryloyloxymethyl] oxetane, and optionally (b4) styrene, N -Phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and poly Copolymers (BI-1) comprising at least one other unsaturated compound selected from the group consisting of methyl methacrylate macromonomers;

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b2) an oxetane unsaturated compound containing 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, and optionally (b4 ) Styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene Copolymers (BI-2) comprising at least one other unsaturated compound selected from the group consisting of macromonomers and polymethylmethacrylate macromonomers;

(b1) an acidic unsaturated compound comprising (meth) acrylic acid, and (b2) an oxetane unsaturated compound containing 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, and (B4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylic Copolymers (BI-3) comprising at least one other unsaturated compound selected from the group consisting of latex, polystyrene macromonomers and polymethylmethacrylate macromonomers;

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b2) an oxetane unsaturated compound containing 3-[(meth) acryloyloxymethyl] -2-phenyloxetane, and optionally (b4 Styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, Copolymers (BI-4) comprising at least one other unsaturated compound selected from the group consisting of polystyrene macromonomers and polymethylmethacrylate macromonomers;

(b1) an acidic unsaturated compound containing (meth) acrylic acid, and (b2) an oxetane unsaturated compound containing 2-[(meth) acryloyloxymethyl] oxetane, and optionally (b4) styrene, N -Phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and poly Copolymers (BI-5) comprising at least one other unsaturated compound selected from the group consisting of methyl methacrylate macromonomers;

(b1) an acidic unsaturated compound comprising (meth) acrylic acid, and (b2) an oxetane unsaturated compound comprising 2-[(meth) acryloyloxymethyl] -4-trifluoromethyloxetane, and (B4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylic The copolymer (BI-6) containing one or more other unsaturated compounds chosen from the group which consists of a latex, a polystyrene macromonomer, and a polymethylmethacrylate macromonomer, etc. are mentioned.

Among these copolymers (BI), copolymers (BI-1), copolymers (BI-2) and the like are particularly preferable.

In the copolymer (B1), the copolymerization ratio of the acidic unsaturated compound is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the oxetane unsaturated compound is preferably 1 to 60% by weight. %, Particularly preferably 10 to 45% by weight, and the copolymerization ratio of the other unsaturated compound is preferably 0 to 70% by weight, more preferably 1 to 70% by weight, particularly preferably 1 to 50% by weight.

In this invention, by making the copolymerization ratio of each unsaturated compound in (B1) copolymer into the said range, it is excellent in storage stability as a liquid composition containing a pigment dispersion liquid and a solvent in addition to sensitivity, solvent resistance, board | substrate adhesiveness, etc. even at high pigment concentration. A radiation sensitive composition can be obtained.

Moreover, as (B2) copolymer, (b1) 1 or more types of acidic unsaturated compound containing (meth) acrylic acid, (b3) tetrahydrofurfuryl (meth) acrylate, and succinic acid [2- (meth) acryloyl Oxyethyl] (tetrahydrofurfuryl) at least one tetrahydrofuran unsaturated compound selected from the group consisting of (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxy At least one other selected from the group consisting of ethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethylmethacrylate macromonomers Preferred are copolymers comprising unsaturated compounds (hereinafter referred to as "copolymers (BII)").

Specific examples of the copolymer (BII) include one or more acidic unsaturated compounds containing, for example, (b1) (meth) acrylic acid, and (b3) one kind of tetrahydrofurfuryl (meth) arcrate. Tetrahydrofuran unsaturated compound and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth Copolymers comprising one or more other unsaturated compounds selected from the group consisting of acrylates, glycerol mono (meth) acrylates, polystyrene macromonomers and polymethylmethacrylate macromonomers (hereinafter referred to as "copolymers (BII-1 ) ";

(b1) at least one acidic unsaturated compound comprising (meth) acrylic acid, and (b3) at least one tetrahydrofuran unsaturated containing succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) Compound, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol Copolymers comprising at least one other unsaturated compound selected from the group consisting of mono (meth) acrylates, polystyrene macromonomers and polymethylmethacrylate macromonomers (hereinafter referred to as "copolymer (BII-2)") Etc. are preferable.

In the copolymer (B2), the copolymerization ratio of the acidic unsaturated compound is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the tetrahydrofuran unsaturated compound is preferably 1 to 70. It is 5% by weight, particularly preferably 5 to 50% by weight, and the copolymerization ratio of the other unsaturated compound is preferably 0 to 80% by weight, more preferably 1 to 80% by weight, particularly preferably 1 to 50% by weight. .

In the present invention, by setting the copolymerization ratio of each unsaturated compound in the (B2) copolymer to the above range, storage stability as a liquid composition containing a pigment dispersion and a solvent, in addition to sensitivity, solvent resistance, adhesion to a substrate, and the like even at a high pigment concentration. This excellent radiation sensitive composition can be obtained.

Examples of the copolymer (B3) include (b1) at least one acidic unsaturated compound containing (meth) acrylic acid, (b3) tetrahydrofurfuryl (meth) acrylate and succinic acid [2- (meth) acryloyloxyethyl] One or more tetrahydrofuran unsaturated compounds selected from the group consisting of (tetrahydrofurfuryl), and (b2) 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3 -Ethyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxy At least one oxetane unsaturated compound selected from the group consisting of methyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and optionally (b4) styrene, N-phenyl Maleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) Copolymers further containing one or more other unsaturated compounds selected from the group consisting of acrylates, glycerol mono (meth) acrylates, polystyrene macromonomers and polymethylmethacrylate macromonomers (hereinafter, "copolymer (BIII) "Is preferred.

As a copolymer (BIII), More specifically, For example, (b1) The acidic unsaturated compound containing (meth) acrylic acid, (b3) The tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate, And (b2) an oxetane unsaturated compound comprising 3-[(meth) acryloyloxymethyl] oxetane, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydrate At least one selected from the group consisting of oxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethylmethacrylate macromonomers Copolymers containing other unsaturated compounds (BIII-1);

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b3) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate, and (b2) 3-[(meth) acryloyloxymethyl ] -3-ethyl oxetane, including oxetane unsaturated compounds, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl ( Copolymers comprising at least one other unsaturated compound selected from the group consisting of meth) acrylates, benzyl (meth) acrylates, glycerol mono (meth) acrylates, polystyrene macromonomers and polymethylmethacrylate macromonomers (BIII) -2);

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b3) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate, and (b2) 3-[(meth) acryloyloxymethyl ] Oxetane unsaturated compound comprising 2-trifluoromethyloxetane, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate And one or more other unsaturated compounds selected from the group consisting of allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethylmethacrylate macromonomers Copolymer (BIII-3);

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b3) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate, (b2) 3-[(meth) acryloyloxymethyl] Oxetane unsaturated compounds, including 2-phenyloxetane, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth (BIII-) A copolymer containing one or more other unsaturated compounds selected from the group consisting of acrylates, benzyl (meth) acrylates, glycerol mono (meth) acrylates, polystyrene macromonomers and polymethylmethacrylate macromonomers 4);

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b3) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate, (b2) 2-[(meth) acryloyloxymethyl] Oxetane unsaturated compounds, including oxetane, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, Copolymers (BIII-5) comprising at least one other unsaturated compound selected from the group consisting of benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethylmethacrylate macromonomers;

(b1) an acidic unsaturated compound containing (meth) acrylic acid, (b3) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate, (b2) 2-[(meth) acryloyloxymethyl] Oxetane unsaturated compounds comprising 4-trifluoromethyloxetane, and optionally (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , Air containing one or more other unsaturated compounds selected from the group consisting of allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethylmethacrylate macromonomers Coalescing (BIII-6) and the like.

Among these copolymers (BIII), copolymer (BIII-1), copolymer (BIII-2) and the like are particularly preferable.

In the copolymer (BIII), the copolymerization ratio of the acidic unsaturated compound is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the tetrahydrofuran unsaturated compound is preferably 1 to 70. The weight ratio, particularly preferably 1 to 40% by weight, the copolymerization ratio of the oxetane unsaturated compound is preferably 1 to 60% by weight, particularly preferably 1 to 40% by weight, and the copolymerization ratio of the other unsaturated compound is preferred. Preferably it is 0 to 70 weight%, More preferably, it is 1 to 60 weight%.

In this invention, the radiation sensitive composition for colored layer formation excellent in the sensitivity, adhesiveness to a board | substrate, solvent resistance, etc. can be obtained by making the copolymerization ratio of each unsaturated compound in a copolymer (BIII) into the said range.

In this invention, another alkali-soluble resin can also be used together with (B1), (B2), and (B3) copolymer.

It does not specifically limit as said other alkali-soluble resin as long as it has solubility with respect to the alkaline developing solution used at the developing process process at the time of forming a colored layer, acting as a binder with respect to (A) coloring agent. For example, an alkali-soluble resin having a carboxyl group (hereinafter referred to as "other carboxyl-containing alkali-soluble resin") is preferably used.

As another carboxyl group-containing alkali-soluble resin, for example, one or more of the carboxyl group-containing unsaturated compounds exemplified for the (B1), (B2) and (B3) copolymers, and the (B1), (B2) and (B3) copolymers The copolymer with 1 or more types of other unsaturated compounds which were illustrated about is mentioned.

As another preferable carboxyl group-containing alkali-soluble resin, More specifically, (i) The carboxyl group-containing unsaturated compound containing (meth) acrylic acid, (ii) Styrene, N-phenylmaleimide, methyl (meth) acrylate, Selected from the group consisting of 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethylmethacrylate macromonomers The copolymer with 1 or more types, etc. are mentioned.

In the present invention, the polystyrene reduced weight average molecular weight (hereinafter, "is measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the (B1), (B2), (B3) copolymer and other alkali-soluble resin. Mw ") are each preferably 3,000 to 300,000, more preferably 5,000 to 100,000.

In addition, the polystyrene reduced horizontal average molecular weight (hereinafter, "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the (B1), (B2), (B3) copolymer and other alkali-soluble resins. Are preferably 3,000 to 60,000, more preferably 5,000 to 25,000.

In the present invention, another alkali-soluble resin having the above-mentioned specific Mw and Mn may be used in combination with the above-mentioned (B1) copolymer having the specific Mw and Mn or (B2) copolymer, or using the (B3) copolymer. By using together, a radiation sensitive composition excellent in developability is obtained, whereby a pixel and a black matrix having sharp pattern edges can be formed, and at the time of development, a residue and a ground are formed on the substrate and the light shielding layer of the unexposed part. Contamination, film residues, etc. are less likely to occur.

Moreover, ratio (Mw / Mn) of Mw and Mn of other alkali-soluble resin with respect to the (B1), (B2), and (B3) copolymer is respectively preferably 1-5, more preferably 1-4.

In this invention, (B1), (B2), (B3) copolymer and another alkali-soluble resin can be used individually or in mixture of 2 or more types, respectively.

In the present invention, the total amount of the alkali-soluble resin 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 colorant (A). If the total amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may be lowered, or background contamination or film residue may be generated on the substrate or the light shielding layer of the unexposed part, while exceeding 1,000 parts by weight. When the colorant concentration is relatively lowered, it may be difficult to achieve the target color density as a thin film.

In addition, the total use ratio of the (B1) copolymer and the (B2) copolymer or the use ratio of the (B3) copolymer in the alkali-soluble resin is preferably 5 to 100% by weight, more preferably 10 to 100% by weight. And particularly preferably 30 to 100% by weight. When the said total use ratio is less than 5 weight%, the desired effect of this invention may be impaired.

In addition, the use ratio of copolymer (B1) with respect to the sum total of (B1) copolymer and (B2) copolymer becomes like this. Preferably it is 1 to 90 weight%, Especially preferably, it is 5 to 80 weight%. When the use ratio of the copolymer (B1) is less than 1% by weight, solvent resistance tends to decrease, while when it exceeds 90% by weight, storage stability tends to decrease.

-(C) polyfunctional monomer-

Multifunctional monomers in the present invention include monomers having two or more polymerizable unsaturated bonds.

As a polyfunctional monomer, For example, Di (meth) acrylate of alkylene glycol, such as ethylene glycol and propylene glycol;

Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and modified dicarboxylic acids thereof;

Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spiran resin;

Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone,

Tris [2- (meth) acryloyloxyethyl] phosphate etc. are mentioned.

Among these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tri Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate, a compound represented by the following formula (3), a compound represented by the following formula (4), and the like, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol Hexaacrylate has high strength of the colored layer, It is especially preferable at the point which is excellent in the surface smoothness of a colored layer, and background contamination, a film | membrane residue, etc. on a board | substrate and a light shielding layer of an unexposed part hardly generate | occur | produce.

The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

The amount of the polyfunctional monomer used in the 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 alkali-soluble resin. If the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, if the amount is more than 500 parts by weight, for example, alkali developability is lowered, or the substrate or light-shielding of the unexposed part is performed. Background contamination, film residues, and the like tend to be easily generated on the layer.

Moreover, in this invention, you may use together the monofunctional monomer which has one polymerizable unsaturated bond with a polyfunctional monomer.

As said monofunctional monomer, the compound similar to the compound illustrated with respect to the acidic unsaturated compound, N-substituted maleimide, or another unsaturated compound in (B) alkali-soluble resin, for example, N- (meth) acryloyl mor M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item other than a polyline, N-vinylpyrrolidone, and N-vinyl- epsilon caprolactam.

These monofunctional monomers can be used individually or in mixture of 2 or more types.

The use ratio of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. When the use ratio of a monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

The total amount of the polyfunctional monomer and the monofunctional 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 alkali-soluble resin. If the total amount of use is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, if the total amount exceeds 500 parts by weight, for example, alkali developability is lowered, or the substrate or the light shielding layer of the unexposed part is reduced. Background contamination, film residues, etc. tend to occur.

-(D) photoinitiator-

The photopolymerization initiator in the present invention can initiate polymerization of the above-mentioned (C) polyfunctional monomer and the monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like. It is a compound that generates active species.

As such a photoinitiator, an acetophenone compound, a biimidazole compound, a triazine compound, a benzoin compound, a benzophenone compound, the (alpha)-diketone compound, a polynuclear quinone compound, a xanthone compound, a diazo compound, O-, for example An acyl oxime compound, an onium salt compound, an imide sulfonate compound, etc. are mentioned. These compounds are components which generate either active radicals or active acids by exposure or both active radicals and active acids.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more thereof. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyl oxime compound are used. At least 1 type selected from is preferable.

In the present invention, the general amount of the photopolymerization initiator is preferably 100 parts by weight of (C) the polyfunctional monomer or 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer (the same when used). 0.01 to 120 parts by weight, more preferably 1 to 100 parts by weight. When the usage-amount of a photoinitiator is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 120 weight part, the coloring formed There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

As a specific example of an acetophenone compound among the preferable photoinitiators in this invention, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2 -Dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione, etc. are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholin) Nophenyl) butan-1-one, 1,2-octanedione and the like are preferred.

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

In this invention, the usage-amount in the case of using an acetophenone compound as a photoinitiator is 100 weight part of (C) polyfunctional monomers or 100 total of (C) polyfunctional monomers and a monofunctional monomer (the same when used, the following) 100 The amount is preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight, still more preferably 1 to 30 parts by weight. When the usage-amount of an acetophenone compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 80 weight part, the coloring formed There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

Moreover, as a specific example of the said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2' -Biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6- Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

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

These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved products and precipitates, and are highly sensitive and sufficiently proceed the curing reaction by exposure of a small amount of energy, and at the same time, the curing reaction in the unexposed part. Since this does not occur, the coated film after exposure is clearly divided into a hardened part insoluble in the developer and an uncured part having high solubility in the developer, whereby a high-precision colored layer pattern without undercuts is disposed according to a predetermined arrangement. Color filters can be formed.

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

In the present invention, the amount of use of the biimidazole compound as the photopolymerization initiator is preferably 100 parts by weight of (C) the polyfunctional monomer or 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 1 to 20 parts by weight. In this case, when the usage-amount of a biimidazole compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, while exceeding 40 weight part When it develops, there exists a tendency which becomes easy to cause the fall of the formed colored layer from the board | substrate, and the film | membrane roughness of the colored layer surface.

In this invention, when using a biimidazole compound as a photoinitiator, using the following hydrogen donor together is preferable at the point which can improve a sensitivity further.

The "hydrogen donor" as used here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole compound by exposure.

As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one mercapto group bonded directly to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, " Mercaptan hydrogen donor ".

The amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as "amine hydrogen Donor ".

On the other hand, these hydrogen donors may have a mercapto group and an amino group simultaneously.

The hydrogen donor will be described in more detail below.

The mercaptan hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocycle, and may have a condensed ring when having two or more of these rings.

In addition, when the mercaptan hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group, and further one As long as the above free mercapto group remains, two sulfur atoms may have a structural unit bonded through a divalent organic group such as an alkylene group, or two sulfur atoms in a disulfide form.

In addition, the mercaptan hydrogen donor may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at portions other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine etc. are mentioned.

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

In addition, the amine hydrogen donor may have one or more benzene rings or heterocycles, and may also have both a benzene ring and a heterocycle, and may have a condensed ring when having two or more of these rings.

In addition, the amine hydrogen donor may be substituted with at least one amino group by an alkyl group or a substituted alkyl group, and may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, etc. It may be substituted.

Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone and 4-dimethylaminopropiophenone. , Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, and the like.

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

On the other hand, the amine hydrogen donor has the function as a sensitizer also in the case of photoinitiators other than a biimidazole compound.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors in that the formed colored layer is hardly eliminated from the substrate during development, and the colored layer strength and sensitivity are also high.

Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'-bis ( Diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, etc. Can be mentioned. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, in particular Preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

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

In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 part by weight based on 100 parts by weight of (C) the polyfunctional monomer or 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. To 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, when the amount of the hydrogen donor exceeds 40 parts by weight, the formed colored layer tends to fall off the substrate during development.

In addition, specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 , 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine , 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl)- Triazine compounds which have halomethyl groups, such as 4, 6-bis (trichloromethyl) -s-triazine, are mentioned.

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

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

In the present invention, the amount of the triazine compound used as the photopolymerization initiator is preferably 0.01 part by weight based on 100 parts by weight of (C) the polyfunctional monomer or 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. To 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the triazine compound used is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged in accordance with a predetermined arrangement. There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

In addition, specific examples of the O-acyl oxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime) and 1- [4- (phenylthio) phenyl ] -Octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H- Carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetyloxime) Etc. can be mentioned.

Among these O-acyl oxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime) and the like are preferred.

The O-acyl oxime compounds may be used alone or in combination of two or more thereof.

In the present invention, the amount of use of the O-acyl oxime compound as the photopolymerization initiator is preferably 100 parts by weight of (C) the polyfunctional monomer or 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. Is 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the usage-amount of an O-acyl oxime compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, and 40 weight part When it exceeds, it exists in the tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

Moreover, as said onium salt compound, a diaryl iodonium salt, a triaryl sulfonium salt, a diaryl phosphonium salt, etc. are mentioned, for example.

As a specific example of the said diaryl iodonium salt, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, diphenyl iodonium hexafluoro arsenate, and diphenyl iodonium tri Fluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodo Hexane hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium tree Fluoroacetate, 4-methoxyphenylphenyl iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumtetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexa Fluoroarsenate, bis (4-tert-butylphen Iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, etc. are mentioned. have.

Specific examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethanesulfonate , Triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate , 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxy Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenylsulfoniumtetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldipe Sulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfoniumtrifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium-p -Toluenesulfonate etc. are mentioned.

As a specific example of the said diaryl phosphonium salt, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron hexafluoro phosphonate etc. are mentioned.

Among these onium salt compounds, diphenyl iodonium hexafluorophosphonate, triphenylsulfonium trifluoromethanesulfonate, and the like are particularly preferable.

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

In the present invention, the amount used when the onium salt compound is used as the photopolymerization initiator is preferably 0.01 to 100 parts by weight of (C) 100 parts by weight of the polyfunctional monomer or 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. To 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the usage-amount of an onium salt compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 40 weight part, the coloring formed There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

-additive-

The radiation sensitive composition for coloring layer formation of this invention can contain various additives as needed.

As said additive, an organic acid or an organic amino compound (except the said hydrogen donor), a hardening | curing agent, a hardening adjuvant, etc. are mentioned, for example.

The said organic acid and organic amino compound are components which show the effect which further suppresses the remainder of the undissolved matter after image development, further improving the solubility to the alkaline developing solution of a radiation sensitive composition.

As said organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has 1 or more carboxyl group in a molecule | numerator is preferable.

As said aliphatic carboxylic acid, For example, monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, 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;

Tricarboxylic acids, such as tricarvalic acid, aconitic acid, and camphoronic acid, etc. are mentioned.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acid in which the carboxyl group is bonded to a phenyl group via a carbon chain.

As a phenyl group containing carboxylic acid, For example, Aromatic monocarboxylic acids, such as benzoic acid, toluic acid, cuminic acid, hemelic acid, and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;

Trivalent or higher aromatic polycarboxylic acids 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, cinnamiledic acid, kumaric acid, and umbelic acid.

Among these organic acids, aliphatic dicarboxylic acid is preferable as the aliphatic carboxylic acid in view of alkali solubility, solubility in a solvent to be described later, prevention of background contamination or film residue on a substrate or a light shielding layer of an unexposed part, In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable. Moreover, as a phenyl group containing carboxylic acid, aromatic dicarboxylic acid is preferable and phthalic acid is especially preferable.

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

The amount of the organic acid to be used is preferably 15% by weight or less, more preferably 10% by weight or less based on the total solid of the radiation-sensitive composition. When the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Moreover, as said organic amino compound, the aliphatic amine or phenyl group containing amine which has 1 or more amino group in a molecule | numerator is preferable.

As said aliphatic amine, it is n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-, for example. Heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4- Mono (cyclo) alkylamines such as methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine and 4-ethylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- di (cyclo) alkylamines such as sec-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri -i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclo Tri (cyclo) alkylamines such as hexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino Mono (cyclo) alkanolamines such as -1-cyclohexanol;

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

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

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2- Cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3- Amino (cyclo) alkanediols such as propanediol and 2-diethylamino-1,3-propanediol;

1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclo Amino group-containing cycloalkanethanols such as hexanemethanol and 4-diethylaminocyclohexanemethanol; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 And aminocarboxylic acids such as -aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Moreover, as said phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, the amino group couple | bonded with the phenyl group through the carbon chain, etc. are mentioned, for example.

As the phenyl group-containing amine, for example, aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline Aromatic amines such as 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and 4-methyl-N, N-dimethylaniline;

Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, and 4-diethylaminobenzyl alcohol;

And aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamine and amino (cyclo) are used as aliphatic amines in view of solubility in a solvent to be described later, prevention of background contamination or film residue on a substrate or a light shielding layer of an unexposed part. Alkanediol is preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propane Diol, 4-amino-1,2-butanediol, etc. are preferable. Moreover, as a phenyl group containing amine, aminophenol is preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol etc. are especially preferable.

The said organic amino compound can be used individually or in mixture of 2 or more types.

The usage-amount of an organic amino compound becomes like this. Preferably it is 15 weight% or less with respect to the whole solid content of a radiation sensitive composition, More preferably, it is 10 weight% or less. When the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

The said hardening | curing agent is a component which hardens these copolymers by reacting with the carboxyl group and / or oxetane ring in the (B1), (B3) copolymer, or the carboxyl group in the (B2) copolymer.

As such a hardening | curing agent, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

As said epoxy compound, a polyfunctional epoxy compound is preferable, As a specific example, Aromatic epoxy resins, such as a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a novolak-type epoxy resin; Other epoxy resins such as cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, and epoxidized oils; In addition to the brominated derivatives of these epoxy resins, epoxides of (co) polymers of butadiene, epoxides of (co) polymers of isoprene, (co) polymers of glycidyl group-containing unsaturated compounds, triglycidyl isocyanurate, and the like can be given. Can be.

Moreover, an epoxy group containing unsaturated compound is also preferable as said epoxy compound, As a specific example, glycidyl (meth) acrylate, 3, 4- epoxy butyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.

Moreover, as said oxetane compound, a polyfunctional oxetane compound is preferable, and as the specific example, bis oxetanyl carbonate, bis oxetanyl adipic acid, bis oxetanyl terephthalate, p-xylylene dicarboxylic acid bis (Co) polymers of low molecular weight compounds such as oxetanyl and 1,4-cyclohexanedicarboxylic acid bisoxetanyl, oxetane ethers of phenol novolak resins, and unsaturated compounds having an oxetane skeleton Polymer compounds such as coalescing (B1) and (B3)).

Moreover, as an oxetane compound, the compound which has both an oxetane ring structure and an unsaturated double bond is also preferable, The said oxetane unsaturated compound is mentioned as the specific example.

These hardeners can be used individually or in mixture of 2 or more types.

The amount of the curing agent used is preferably 30% by weight or less, and more preferably 20% by weight or less based on the total solid of the radiation-sensitive composition. When the usage-amount of a hardening | curing agent exceeds 30 weight%, there exists a tendency for the storage stability of the radiation sensitive composition obtained to fall.

The said hardening adjuvant is a component which accelerates | stimulates the hardening reaction by the said hardening | curing agent by ring-opening the epoxy group and / or oxetane ring which the said hardening | curing agent has.

As such a hardening adjuvant, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an amino compound, a thermal acid generator, etc. are mentioned, for example.

As a specific example of the said polyhydric carboxylic acid, the thing similar to the compound which has two or more carboxyl groups in the said organic acid is mentioned. As a specific example of the said amino compound, the thing similar to the said organic amino compound is mentioned.

Moreover, as a specific example of the said polyhydric carboxylic anhydride, aromatic polyhydric carboxylic acids, such as phthalic anhydride, a pyromellitic dianhydride, a trimellitic anhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, are mentioned. anhydride; Aliphatic polyhydric carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvalylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ; Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polyhydric carboxylic acid anhydrides such as water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride; In addition to ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitate anhydride and glycerin tristrimellitate anhydride, Adeka Hardner EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), lycaside HH Epoxy resin hardening | curing agent etc. which are marketed by brand names, such as (the manufacture) and MH-700 (made by Shin-Nippon Rika Co., Ltd.), are mentioned.

Moreover, as said thermal acid generator, a sulfonium salt (except the triarylsulfonium salt described with respect to the said (D) photoinitiator), a benzothiazonium salt, an ammonium salt, a phosphonium salt, a sulfonic acid ester compound, for example And sulfonimide compounds, diazomethane compounds and the like. Among these, sulfonium salts, benzothiazonium salts, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds and the like are preferable.

Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium Hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4 Alkylsulfonium salts such as acetoxyphenylsulfonium hexafluoroantimonate;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroarsenate and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroan thimonate, dibenzyl 4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5- dibenzylsulfonium salts such as tert-butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzyl sulfonium salts, such as an antimonate and o-chlorobenzyl-3- chloro-4- hydroxyphenyl methyl sulfonium hexafluoro antimonate, etc. are mentioned.

In addition, specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p- Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, etc. Benzyl benzothiazonium salt etc. are mentioned.

Moreover, as a specific example of the said sulfonic acid ester compound, benzoin tosylate, the (alpha)-methylol benzo intosylate, the (alpha)-methylol benzoin n-octane sulfonate, a pyrogallol tris (trifluoromethane sulfonate), a pyrogallol Tris (nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10- diethoxyanthracene-2-sulfonate, and the like.

In addition, specific examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene- 2,3-dicarboxyimide, N- (10-campasulfonyloxy) succinimide, N- (10-campasulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboxyimide, N-[(5-methyl-5-carboxy methanebicyclo [2.2.1] hepta-2-yl) sulfonyloxy] succinimide, etc. are mentioned.

In addition, specific examples of the diazomethane compound include bis (cyclohexanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane and bis (1,4-dioxaspiro [4.5] -decane-7. -Sulfonyl) diazomethane, etc. are mentioned.

Among these thermal acid generators, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoro Antimonate, Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, N -(Trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and the like are preferred.

The said hardening adjuvant can be used individually or in mixture of 2 or more types.

The usage-amount of a hardening adjuvant becomes like this. Preferably it is 15 weight% or less with respect to the whole solid content of a radiation sensitive composition, More preferably, it is 10 weight% or less. When the usage-amount of a hardening adjuvant exceeds 15 weight%, there exists a tendency for the storage stability of the obtained radiation sensitive composition to fall, or the colored layer formed to fall easily from a board | substrate at the time of image development.

Moreover, as an additive of that excepting the above, For example, Dispersion adjuvant, such as blue pigment derivatives, such as a copper phthalocyanine derivative, and a yellow pigment derivative;

Fillers such as glass and alumina;

Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether, and poly (fluoroalkyl acrylate);

Surfactants, such as nonionic, cationic, and anionic:

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter;

Antioxidants such as 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone;

Aggregation inhibitors such as sodium polyacrylate;

And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

menstruum

Although the radiation sensitive composition of this invention makes the said (A)-(D) component an essential component, and contains the said additive component as needed, it is normally manufactured as a liquid composition by mix | blending a solvent.

As said solvent, it can select suitably and can use, as long as it does not react with these components, disperse | distributing or dissolving (A)-(D) component and additive component which comprise a radiation sensitive composition, and have moderate volatility.

As such a solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri (Poly) alkylenes such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether Recall monoalkyl ether;

(Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; 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;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutane, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, in view of solubility, pigment dispersibility, coating properties, etc. Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3-methyl-3 Methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, ethyl butyrate i-propyl, n-butyl butyrate, ethyl pyruvate, and the like. desirable.

The said solvent can be used individually or in mixture of 2 or more types.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, together with the solvent High boiling point solvents, such as diethyl oxalate, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.

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

Although the usage-amount of a solvent is not specifically limited, From a viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition becomes like this. Preferably it is 5-50 weight%, More preferably, It is preferable that the amount is 10 to 40% by weight.

Color filter

The color filter of this invention is equipped with the colored layer formed using the radiation sensitive composition of this invention.

Below, the method of forming the colored layer in the color filter of this invention is demonstrated.

First, a light shielding layer is formed on the surface of a substrate so as to partition a part which forms a pixel as needed, and for example, after apply | coating the liquid composition of the radiation sensitive composition which red pigment disperse | distributed on this board | substrate, it is free. Baking is performed to evaporate the solvent to form a coating film.

Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and then post-bakes to form the pixel array in which the red pixel pattern was arrange | positioned in the predetermined arrangement.

Thereafter, using the liquid composition of each radiation-sensitive composition in which the green or blue pigment is dispersed, the liquid pixel composition and the blue pixel array and the blue color are applied in the same manner as described above by applying, prebaking, exposing, developing and post-baking the liquid composition. By sequentially forming pixel arrays on the same substrate, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, a black matrix can be formed similarly to the case of said pixel formation using the liquid composition of the radiation sensitive composition which black pigment disperse | distributed, for example.

As a board | substrate used when forming a pixel and / or a black matrix, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like.

When the liquid composition of the radiation sensitive composition is applied to a substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating or inkjet may be employed. In particular, the spin coating method and the slit die coating method are preferable.

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

As radiation used for forming the pixel and / or black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. may be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable. .

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

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

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. On the other hand, after alkali development, it washes with water preferably.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid soaking) developing method, and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

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

Color liquid crystal display element

The color liquid crystal display element of this invention is equipped with the color filter of this invention.

Moreover, as one form of the color liquid crystal display element of this invention, it forms especially a pixel and / or a black matrix on the thin film transistor substrate array as above-mentioned using the radiation sensitive composition of this invention, and has especially excellent characteristic. A color liquid crystal display element can be manufactured.

Although the radiation sensitive composition of this invention contains the said (A)-(D) component as an essential component, it will be as follows (a)-(j), if an especially preferable composition is concretely illustrated.

(a) The radiation sensitive composition for forming a colored layer in which (B1) copolymer contains copolymer (BI) and (B2) copolymer contains copolymer (BII).

(b) The copolymer (BI) contains at least one member selected from the group consisting of copolymers (BI-1) to (BI-6), and the copolymer (BII) is a copolymer (BII-1) and air. The radiation sensitive composition for colored layer formation of said (a) containing 1 or more types chosen from the group which consists of coalescence (BII-2).

(c) Said (a) or (b) in which (C) polyfunctional monomer contains 1 or more types chosen from the group of trimethylol propane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. The radiation sensitive composition for colored layer formation of this.

(d) the above (a), (b) or (c) wherein the photopolymerization initiator comprises at least one member selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds and O-acyl oxime compounds A radiation-sensitive composition for forming a colored layer of).

(e) The radiation sensitive composition for colored layer formation of said (a), (b), (c) or (d) whose (A) coloring agent contains an organic pigment or carbon black.

(f) The radiation sensitive composition for colored layer formation in which (B) alkali-soluble resin contains a copolymer (BII).

(g) The radiation sensitive composition for colored layer formation of said (f) in which copolymer (BII) contains 1 or more types chosen from the group of copolymer (BII-1)-(BII-2).

(h) Said (f) or (g) in which (C) polyfunctional monomer contains 1 or more types chosen from the group of trimethylol propane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. The radiation sensitive composition for colored layer formation of this.

(i) Persimmon for forming the colored layer of (f), (g) or (h) above, wherein the photopolymerization initiator comprises at least one member selected from the group consisting of acetophenone compounds, biimidazole compounds, and triazine compounds. Radioactive composition.

(j) The radiation sensitive composition for colored layer formation of said (f), (g), (h) or (i) whose (A) coloring agent contains an organic pigment or carbon black.

In addition, the preferred color filter of the present invention

(k) The pixel and / or black matrix formed using the radiation sensitive composition for colored layer formation of said (a), (b), (c), (d) or (e) is provided.

(l) The pixel and / or black matrix formed using the radiation sensitive composition for colored layer formation of said (f), (g), (h), (i) or (j) is provided.

Moreover, the preferable color liquid crystal display element of this invention is

(m) comprising the color filter of (k) or (l) above,

The more preferable color liquid crystal display element of this invention is

(n) The color filter of said (k) or (l) is provided on the thin film transistor substrate array.

As described above, the radiation-sensitive composition of the present invention maintains good sensitivity, resolution, pattern shape, and the like, and particularly has good storage stability as a liquid composition, and also has excellent solvent resistance to a wide range of solvents, adhesion to a substrate, and the like. And a black matrix pattern.

Therefore, the radiation sensitive composition of this invention can be used very favorably for manufacture of various color filters including the color filter for color liquid crystal display elements in the electronic industry.

<Example>

Hereinafter, an Example is given and this invention is demonstrated further more concretely. However, the present invention is not limited to the following examples. Where parts and% are based on weight.

Synthesis of Alkali Soluble Copolymers

Synthesis Example 1

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetates were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 3- (methacryloyloxymethyl 25 parts of) -3-ethyl oxetane, 60 parts of benzyl methacrylates, and 3 parts of (alpha) -methylstyrene dimers were added as a molecular weight modifier, and it substituted by nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-1)".

Synthesis Example 2

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetates were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 3- (methacryloyloxymethyl 25 parts of) -3-ethyl oxetane, 20 parts of N-phenylmaleimide, 10 parts of styrene, 30 parts of benzyl methacrylate, and 3 parts of (alpha) -methylstyrene dimers were added as a molecular weight regulator, and it carried out by nitrogen substitution. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-2)".

Synthesis Example 3

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetates were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 3- (methacryloyloxymethyl ) 25 parts of oxetane, 60 parts of benzyl methacrylate, and 3 parts of (alpha) -methylstyrene dimers were added as a molecular weight modifier, and it substituted by nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-3)".

Synthesis Example 4

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 25 parts of tetrahydrofurfuryl methacrylate. , 60 parts of benzyl methacrylate, and 3 parts of (alpha) -methylstyrene dimers were added as a molecular weight modifier, and it substituted by nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-4)".

Synthesis Example 5

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 25 parts of tetrahydrofurfuryl methacrylate. 20 parts of N-phenylmaleimide, 10 parts of styrene, 30 parts of benzyl methacrylate, and 3 parts of α-methylstyrene dimer were added as a molecular weight modifier and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-5)".

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added, followed by 15 parts of methacrylic acid, 60 parts of benzyl methacrylate, and n-. 25 parts of butyl methacrylates and 3 parts of (alpha) -methylstyrene dimers were added as a molecular weight modifier, and it substituted by nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-6)".

Synthesis Example 7

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 15 parts of tetrahydrofurfuryl methacrylate. 15 parts of 3- (methacryloyloxymethyl) -3-ethyloxetane, 55 parts of benzyl methacrylate, and 3 parts of α-methylstyrene dimer were added as a molecular weight modifier and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and the resin solution was obtained by maintaining the temperature for 5 hours to polymerize. This resin was referred to as "alkali-soluble resin (B-7)".

Synthesis Examples 8 to 14 and Comparative Synthesis Examples 1 to 6

Except having changed the unsaturated compound which comprises alkali-soluble resin into the kind and quantity shown in Table 1, it carried out similarly to the synthesis example 7, and obtained each solution of alkali-soluble resin (B-8)-(B-20).

Preparation of Pigment Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 177 = 80/20 (weight ratio) 20 parts of mixtures, 5 parts of BYK-2001 as a dispersant (solid content conversion), and 75 parts of propylene glycol monomethyl ether acetate as a solvent were processed by the bead mill, and the pigment dispersion (R) was prepared. Prepared.

Preparation Example 2

(A) As a coloring agent, C.I. Pigment Green 36 / C.I. Pigment Yellow 150 = 50/50 (weight ratio) 20 parts of mixtures, 5 parts (in terms of solids) of Solpas 24000 as a dispersant, and 75 parts of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to give a pigment dispersion (G). Was prepared.

Example 1

100 parts of the pigment dispersion liquid (R), 10 parts (solid content conversion) as a solution obtained in Synthesis Example 1, and 5 parts (a solution obtained in the synthesis example 4 as the solution obtained in Synthesis Example 4). Solid content conversion), (C) 15 parts of trimethylolpropane triacrylate as a polyfunctional monomer, (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- as a photoinitiator- 5 parts of 1-one, 3 parts of diethyl thioxanthone, and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R-1) having a solid content concentration of 25% (see Table 2 below).

The liquid composition (R-1) was patterned and evaluated according to the following procedure. The evaluation results are shown in Table 10 below.

Formation of patterns

After apply | coating a liquid composition (R-1) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 4 minutes, and formed the coating film of 1.3 micrometers in film thicknesses. Then, three board | substrates were cooled to room temperature, and it exposed by the exposure amount of 2,000 J / m <2> to the coating film on each board | substrate through a photomask using the high pressure mercury lamp for the coating film on each board | substrate. Thereafter, a shower development was performed by discharging a 0.04% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) to the coating films on each substrate, followed by post-baking at 220 ° C. for 30 minutes to obtain 200 × 200. A dot pattern of 탆 was formed.

Solvent resistance evaluation

Three substrates exposed at an exposure dose of 2,000 J / m 2 were N-methylpyrrolidone at 25 ° C (described as "NMP" in Tables 10 to 13), and 18% aqueous HCl solution ("HCl" in Tables 10 to 13). Immersed in a 5% aqueous KOH solution (described as "KOH" in Tables 10 to 13) for 30 minutes, and the dot pattern before and after immersion was observed with a scanning electron microscope, and the pattern was formed well and before and after immersion. ? When the film thickness ratio (film thickness after immersion x 100 / film thickness before immersion) is 95% or more, and when the film thickness ratio before and after immersion is less than 95% or when a defect is seen in a part of the pattern. The case where all peeled from the board | substrate was evaluated as x.

Adhesion Evaluation

After apply | coating a liquid composition (R-1) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 4 minutes, and formed the coating film of 1.3 micrometers in film thicknesses. Then, after cooling this board | substrate to room temperature, it exposed to the coating film by the exposure amount of 2,000 J / m <2> using the high pressure mercury lamp. Thereafter, shower development was performed by discharging a 0.04% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) to the coating film, followed by post-baking at 220 ° C. for 30 minutes. Thereafter, the coating film is cross-cut into 100 checkerboard grid shapes in accordance with JIS K5400 standard to perform an adhesion test, and the case where 1 to 10 of the checkerboard scales does not occur is checked. The case where peeling more than these 10 pieces was evaluated as x.

Evaluation of Storage Stability of Liquid Compositions

When liquid composition (R-1) was put into a glass bottle and preserve | saved for 1 week in a 40 degreeC constant temperature and humidity tank, the viscosity before and after storage was measured, and the viscosity change rate (viscosity after storage x100 / viscosity before storage) was computed. . On the other hand, the viscosity of the pigment dispersion liquid R used here, the solution viscosity of alkali-soluble resin (B-1), and the solution viscosity of alkali-soluble resin (B-4) did not show a change even if it preserve | saved on the same conditions as the above.

Examples 2 to 22

In Example 1, liquid compositions (R-2) to (R-22) were prepared in the same manner as in Example 1 except that the type and amount of the constituent components were changed as shown in Table 2 or Table 3. .

Next, it evaluated similarly to Example 1 except having used liquid compositions (R-2)-(R-22) instead of liquid composition (R-1), respectively. On the other hand, the solution viscosity of alkali-soluble resin (B-5) used in Examples 8-10, the solution viscosity of alkali-soluble resin (B-2) used in Examples 11-16, and alkali-soluble resin used in Examples 17-22 The solution viscosity of (B-3) was not changed even when stored under the same conditions as in the storage stability evaluation of the liquid composition. The evaluation results are shown in Table 10.

Example 23

100 parts of pigment dispersion (G), 10 parts (solid content conversion) as a solution obtained in Synthesis Example 1, and 5 parts (as a solution obtained in Synthesis Example 4) as alkali solution (B-4) Solid content conversion), (C) 12 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- as a photoinitiator 5 parts of 1-one, 3 parts of 4,4'-bis (diethylamino) benzophenone, and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (G-1) having a solid content concentration of 25% (following). See Table 4).

Next, except having used the liquid composition (G-1) instead of the liquid composition (R-1), it carried out similarly to Example 1, and formed the pattern and evaluated. On the other hand, even if the viscosity of the pigment dispersion (G) used here was preserve | saved on the same conditions as the case in the storage stability evaluation of the said liquid composition, a change was not seen. The evaluation results are shown in Table 11 below.

Examples 24-44

In Example 23, liquid compositions (G-2) to (G-22) were prepared in the same manner as in Example 23 except that the type and amount of the constituent components were changed as shown in Table 4 or Table 5. .

Next, it evaluated similarly to Example 1 except having used liquid compositions (G-2)-(G-22) instead of liquid composition (R-1), respectively. The evaluation results are shown in Table 11.

Comparative Examples 1 to 19

In Example 1, liquid compositions (R-23) to (R-41) were prepared in the same manner as in Example 1 except that the type and amount of the constituents were changed as shown in Table 6 or Table 7. It was.

Next, it evaluated similarly to Example 1 except having used liquid compositions (R-23)-(R-41) instead of liquid composition (R-1), respectively. The evaluation results are shown in Table 12 below.

Comparative Examples 20 to 38

In Example 23, liquid compositions (G-23) to (G-41) were prepared in the same manner as in Example 23 except that the kind and amount of the constituents were changed as shown in Table 8 or Table 9 below. It was.

Next, it evaluated like Example 1 except having used liquid compositions (G-23)-(G-41) instead of liquid composition (R-1), respectively. The evaluation results are shown in Table 13 below.

In Tables 2-9, the content of a polyfunctional monomer, a photoinitiator, and an additive is as follows.

Polyfunctional monomer

C-1: trimethylolpropane triacrylate

C-2: dipentaerythritol hexaacrylate

Photopolymerization initiator

D-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

D-2: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime)

D-3: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one

D-4: 2,4-diethyl thioxanthone

D-5: 4,4'-bis (diethylamino) benzophenone

additive

E-1: bisphenol A novolak-type epoxy resin (brand name 157S65, Japan epoxy resin Co., Ltd. product)

E-2: trimellitic anhydride

E-3: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide

Example 45

100 parts of pigment dispersion (R), alkali-soluble resin (B-7) as a resin solution obtained in Synthesis Example 7 (parts in terms of solid content), (C) dipentaerythritol hexaacrylate as a polyfunctional monomer, and 10 parts of trimethyl 5 parts of all propane triacrylate, (D) 5 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 4,4'-bis as a photoinitiator 3 parts of (diethylamino) benzophenone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R-42) having a solid content concentration of 25% (see Table 14 below).

The liquid composition (R-42) was evaluated by forming a pattern according to the following procedure. The evaluation results are shown in Table 18 below.

Formation of patterns

After apply | coating a liquid composition (R-42) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 4 minutes, and formed the coating film with a film thickness of 1.3 micrometers. Then, three board | substrates were cooled to room temperature, and it exposed by the exposure amount of 2,000 J / m <2> to the coating film on each board | substrate through a photomask using the high pressure mercury lamp for the coating film on each board | substrate. Subsequently, shower development was performed by discharging a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) to the coating films on each substrate. A dot pattern of 200 mu m was formed.

Solvent resistance  evaluation

Three substrates exposed at an exposure dose of 2,000 J / m 2 were subjected to N-methylpyrrolidone at 25 ° C. (described as “NMP” in Tables 18 and 19), and an aqueous 18% HCl solution in Table 18 and Table 19. HCl ”) or 5% aqueous KOH solution (described as“ KOH ”in Tables 18 and 19) for 30 minutes, and the dot pattern before and after immersion was observed with a scanning electron microscope to obtain a good pattern. Is formed and the film thickness ratio before and after immersion (film thickness after immersion x 100 / film thickness before immersion) is 95% or more, and the film thickness ratio before and after immersion is less than 95% or when a defect is seen in a part of the pattern. (Triangle | delta) and the case where all the patterns peel from a board | substrate after immersion were evaluated as x.

Adhesion Evaluation

After apply | coating a liquid composition (R-42) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 4 minutes, and formed the coating film with a film thickness of 1.3 micrometers. Then, after cooling this board | substrate to room temperature, it exposed to the coating film by the exposure amount of 2,000 J / m <2> using the high pressure mercury lamp. Thereafter, shower development was performed by discharging a 0.04% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) to the coating film, followed by post-baking at 220 ° C. for 30 minutes. Thereafter, the coating film is cross-cut into 100 checkerboard grid shapes in accordance with JIS K5400 standards to perform an adhesion test, and the case where 1 to 10 of the checkerboard scales does not occur is checked. The case where peeling more than these 10 pieces was evaluated as x.

Evaluation of Storage Stability of Liquid Compositions

When the liquid composition (R-42) was placed in a glass bottle and stored for one week in a constant temperature and humidity chamber at 40 ° C, the viscosity before and after storage was measured to calculate the rate of change of viscosity (viscosity after preservation x 100 / viscosity before storage). It was. On the other hand, even if the viscosity of the pigment dispersion (R) and the solution viscosity of the alkali-soluble resin (B-7) used here were stored under the same conditions as above, no change was observed.

Examples 46-56

In Example 45, except having changed the constituent components as shown in Table 14, the liquid compositions (R-43) to (R-53) were prepared in the same manner as in Example 45.

Next, it evaluated similarly to Example 45 except having used liquid compositions (R-43)-(R-56) instead of liquid composition (R-42), respectively. On the other hand, the solution viscosity of alkali-soluble resins (B-8) to (B-14) used in Examples 50 to 53 showed no change even when stored under the same conditions as in the storage stability evaluation of the liquid composition. The evaluation results are shown in Table 18.

Example 57

100 parts of pigment dispersion liquid (G), 15 parts (solid content conversion) as resin solution obtained by the synthesis example 7, and (C) dipentaerythritol hexaacrylate 5 parts and penta as a polyfunctional monomer 10 parts of erythritol tetraacrylate, (D) 5 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and 5 parts of diethyl thioxanthone as photoinitiators Propylene glycol monomethyl ether acetate was mixed as a solvent to prepare a liquid composition (G-42) having a solid content concentration of 25%.

Subsequently, a pattern was formed and evaluated in the same manner as in Example 45 except that the liquid composition (G-42) was used instead of the liquid composition (R-42). On the other hand, even if the viscosity of the pigment dispersion (G) used here was preserve | saved on the same conditions as the case in the storage stability evaluation of the said liquid composition, a change was not seen. The evaluation results are shown in Table 18.

Examples 58-68

In Example 57, except for changing the constituent components as shown in Table 15 below, liquid compositions (G-43) to (G-53) were prepared in the same manner as in Example 57.

Next, it evaluated like Example 45 except having used liquid compositions (G-43)-(G-53) instead of liquid composition (R-42), respectively. The evaluation results are shown in Table 18.

Comparative Examples 39 to 48

In Example 45, liquid compositions (R-54) to (R-63) were prepared in the same manner as in Example 45 except for changing the components as shown in Table 16 below.

Next, it evaluated similarly to Example 45 except having used liquid compositions (R-54)-(R-63) instead of liquid composition (R-42), respectively. The evaluation results are shown in Table 19 below.

Comparative Examples 49 to 58

In Example 57, except for changing the constituent components as shown in Table 17, the liquid compositions (G-54) to (G-63) were prepared in the same manner as in Example 57.

Next, it evaluated similarly to Example 45 except having used liquid compositions (G-54)-(G-63) instead of liquid composition (R-42), respectively. The evaluation results are shown in Table 19.

In Tables 14-17, the content of a polyfunctional monomer, a photoinitiator, and an additive is as follows.

Multifunctional  Monomer

C-1: dipentaerythritol hexaacrylate

C-2: trimethylolpropane triacrylate

C-3: pentaerythritol tetraacrylate

Photopolymerization Initiator

D-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

D-2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one

D-3: 4,4'-bis (diethylamino) benzophenone

D-4: 2,4-diethyl thioxanthone

additive

E-1: bisphenol A novolak-type epoxy resin (brand name 157S65, Japan epoxy resin Co., Ltd. product)

E-2: trimellitic anhydride

E-3: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide

The radiation-sensitive composition of the present invention maintains good sensitivity, resolution, pattern shape, and the like, and in particular, has a good storage stability as a liquid composition, a pixel pattern and a black matrix pattern that also have excellent solvent resistance to a wide range of solvents, adhesion to a substrate, and the like. Can be formed.

Claims (5)

(A) A radiation sensitive composition containing a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (B) alkali-soluble resin is (b1) unsaturated carboxylic acid, unsaturated At least one first unsaturated compound selected from the group consisting of carboxylic anhydrides and unsaturated phenol compounds, (b2) unsaturated compounds having an oxetane skeleton, and (b3) unsaturated compounds having a tetrahydrofuran skeleton A radiation sensitive composition comprising a copolymer of at least one second unsaturated compound, wherein the radiation sensitive composition is used to form a colored layer. (B) Alkali-soluble resin is a copolymer of the unsaturated compound which has an oxetane frame | skeleton as a 1st unsaturated compound and a 2nd unsaturated compound, or the tetrahydrofuran skeleton as a 1st unsaturated compound and a 2nd unsaturated compound. A radiation sensitive composition which is a copolymer of an unsaturated compound having. The radiation-sensitive composition according to claim 1, wherein the alkali-soluble resin (B) is a copolymer of an unsaturated compound having an oxetane skeleton as the first unsaturated compound and a second unsaturated compound and an unsaturated compound having a tetrahydrofuran skeleton. The color filter provided with the colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-3. The color liquid crystal display element provided with the color filter of Claim 4.