TWI444767B - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Description

Radiation-sensitive composition for forming a coloring layer, filter and color liquid crystal display device

The present invention relates to a radiation-sensitive composition, a filter, and a color liquid crystal display device for forming a coloring layer. In particular, it relates to a radiation-sensitive composition for forming a colored layer, which can be used for filters for transmission and reflection type color liquid crystal displays and color photographic devices, which are sensitive to radiation. A color filter for forming a coloring layer of a composition and a color liquid crystal display device comprising the same.

As a method of producing a filter using a colored radiation-sensitive composition, a substrate in which a colored radiation-sensitive composition is applied to a substrate or a light-shielding layer having a desired pattern is known, dried, and then dried to be coated. A method of exposing radiation of a desired pattern (hereinafter referred to as "exposure") and developing to obtain a color pixel (refer to JP-A 2-144502 and JP-A 3-53201) (the term "JP-A" used in the present invention "This is the "Japanese Patent Application Disclosure").

In the technical field of filters, the tact time is usually shortened by reducing the exposure amount, and the pixels and black matrix formed by a small amount of exposure need to have excellent pattern, solvent resistance and adhesion to the substrate. Sex. However, when the exposure amount is low, the prior art colored radiation-sensitive composition tends to have problems such as a decrease in film retention after exposure, a loss of pattern portion, side etching, and peeling of the pattern from the substrate. Therefore, when the process time is shortened, it is difficult to obtain a satisfactory pixel pattern and black matrix pattern from the prior art colored radiation-sensitive composition. Solvent resistance of prior art radiation sensitive compositions and adhesion to substrates are also unsatisfactory. In addition, the colored radiation-sensitive composition used to form the filter has a high level of pigment for high color reproducibility. In terms of production control of the filter, in addition to the storage stability of the pigment dispersion and the storage stability of the solvent-containing liquid composition, the alkali-soluble resin itself also needs to have high storage stability. However, prior art colored radiation-sensitive compositions do not fully meet these requirements.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel radiation-sensitive composition for forming a coloring layer which, when the pigment content is high, the storage stability of the alkali-soluble resin itself, the storage stability of the pigment dispersion, and the storage of the liquid composition The stability is extremely excellent, and even if the exposure amount is low, there is no problem that the film retention is lowered, the edge portion of the pattern is missing, and the side etching is caused, and the pixel and the black matrix having excellent solvent resistance and adhesion to the substrate are provided.

Another object of the present invention is to provide a filter having a coloring layer formed from the composition of the present invention and a color liquid crystal display device comprising the same.

Other objects and advantages of the invention will be apparent from the description.

According to the present invention, the foregoing objects and advantages are first attained by a radiation-sensitive composition for forming a colored layer comprising (A) a colorant, (B) an alkali-soluble resin, and (c) polyfunctionality. a monomer and (D) photopolymerization initiator, wherein the alkali-soluble resin (B) comprises (b1) at least one member selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and an unsaturated phenol compound, and (b2) has An unsaturated compound of an alicyclic carbocyclic structure and (b3) a copolymer of an unsaturated compound having a propylene oxide ring structure.

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

In accordance with the present invention, secondly, the foregoing objects and advantages of the present invention are achieved by a filter having a coloring layer formed from the aforementioned radiation-sensitive composition for forming a colored layer.

According to the present invention, the third point is that the above objects and advantages of the present invention are achieved by a color liquid crystal display device including the foregoing filter.

Detailed description of preferred embodiments

The invention will be described in detail below.

Radiation-sensitive composition for forming a colored layer

- (A) Colorant - The coloring agent in the present invention is not limited to a specific color, and is appropriately selected depending on the application purpose of the produced filter. It can be a pigment, a dye or a natural coloring matter.

Because of the high color and color resistance and the heat resistance of the filter, a coloring agent with high color rendering property and high heat resistance, especially a coloring agent having high heat decomposition resistance, is preferred for the present invention. Colorant. Therefore, it is preferred to use an organic pigment or an inorganic pigment, and it is particularly preferable to use an organic pigment or carbon black.

Examples of the foregoing organic pigments are compounds classified as a group of pigments according to a colorimetric index (CI; published by The Society of Dyers and Colourists), especially a compound having the following color index (CI) number: CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 180 and CI Pigment Yellow 185; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36. CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71 and CI pigment orange 73; CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36 and CI pigment violet 38; CI pigment red 1, CI pigment red 2. CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, C.1. Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 50:1, CI Pigment Red 52:1, CI Pigment Red 53:1, CI Pigment Red 57, CI Pigment Red 57:1, CI Pigment Red 57:2, CI Pigment Red 58:2 , CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81:1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90:1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, C.1. Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 15 1. CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264 and CI Pigment Red 265; CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15 : 6 and CI Pigment Blue 60; CI Pigment Green 7 and CI Pigment Green 36; CI Pigment Brown 23 and CI Pigment Brown 25; and CI Pigment Black 1 and CI Pigment Black 7.

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

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

In the present invention, the aforementioned organic pigments and inorganic pigments may be used singly or in combination of two or more kinds, or may be used in combination. For example, it is preferred to form a pixel using one or more organic pigments, and it is preferred to form a black matrix using two or more organic pigments and/or carbon black.

In the present invention, the surface of the pigment particles may be modified with a polymer as appropriate before use. Examples of the polymer used to modify the surface of the pigment particles include the polymers disclosed in JP-A 8-259876 and commercially available polymers and oligomers for dispersing pigments.

In the present invention, the colorant may optionally be used in combination with a dispersing agent. The dispersant is, for example, a cationic, anionic, nonionic, amphoteric, or a surfactant based on polyfluorene as a substrate or a fluorine-based substrate.

Examples of the foregoing surfactant include polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, and polyethylene oxide oleyl ether; polyethylene oxide Alkyl phenyl ethers such as polyethylene oxide n-octyl phenyl ether and polyethylene oxide n-decyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and poly Ethylene glycol distearate; sorbitan fatty acid ester; polyester modified with fatty acid; polyurethane modified with tertiary amine; and polyethylenimine. Commercially available trade names of such surfactants are KP (Shin-Etsu Chemical, Co., Ltd.), Polyflow (Kyoeisya Kagaku Co., Ltd.), F Top (Tokem Products Co., Ltd.), Megafac ( Dainippon Ink and Chemicals, Inc.), Florade (Sumitomo 3M Limited), Asahi Guard and Surflon (Asahi Glass Co., Ltd.), BYK and Disperbyk (BYK Chemie Japan KK), and Solsperse (Seneka Co., Ltd.).

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

In the present invention, the radiation-sensitive resin composition can be produced by a suitable method. When a pigment is used as the colorant, it is preferably mixed with a solvent in the presence of a dispersant and dispersed therein, while being milled by a bead mill or a roll mill to prepare a pigment dispersion, which is described below. The components (B), (C) and (D) are optionally mixed with additional solvents and additives to prepare a radiation-sensitive resin composition.

The amount of the dispersant used to prepare 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 to 50, based on 100 parts by weight of the pigment. Parts by weight. When the amount of the dispersant is more than 100 parts by weight, developability may be impaired.

The solvent used to prepare the pigment dispersion may be the same as the solvent used in the preparation of the liquid radiation-sensitive resin composition described below.

The amount of the solvent used to prepare the pigment dispersion is preferably from 200 to 1,000 parts by weight, more preferably from 300 to 800 parts by weight, per 100 parts by weight of the pigment.

When a pigment dispersion is prepared using a bead mill, a glass pigment or a titanium oxide bead having a diameter of about 0.5 to 10 mm is mixed and dispersed with a pigment solution, preferably, with cooling water or the like. The solution contains a pigment, a solvent, and a dispersing agent.

The filling rate of the beads is preferably from 50 to 80% of the mill capacity, and the injection amount of the pigment-mixed solution is preferably about 20 to 50% of the mill capacity. The treatment time is preferably from 2 to 200 hours, more preferably from 2 to 100 hours.

The pigment dispersion is prepared using a roll mill by mixing and dispersing the pigment-mixed solution using a three-roll mill or a two-roll mill, preferably while cooling with cooling water or the like.

The spacing between the rolls is preferably 10 microns or less and the shear force is typically about 10 ⁸ dynes/second. The treatment time is preferably from 2 to 50 hours, more preferably from 2 to 25 hours.

- (B) alkali-soluble resin - the alkali-soluble resin in the present invention contains (b1) at least one member selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and an unsaturated phenol compound (these compounds are hereinafter referred to as "acid unsaturated" Compound "), (b2) an unsaturated compound having an alicyclic carbon ring structure (hereinafter referred to as "alicyclic unsaturated compound") and (b3) an unsaturated compound having a propylene oxide ring structure (hereinafter referred to as " A copolymer of a propylene oxide unsaturated compound (hereinafter referred to as "copolymer (BI)"). The component (B) is used as a binder of the colorant (A), and has solubility in an alkali developer in a developing step for forming a coloring layer.

Examples of the aforementioned unsaturated carboxylic acid and unsaturated carboxylic anhydride include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids and anhydrides thereof such as cis-butane Alkenedioic acid, maleic anhydride, fumaric acid, isaconic acid, isaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; unsaturated polycarboxylic acid having three or more carboxyl groups and An anhydride; a mono[(meth)acryloxyalkyl] ester of a polycarboxylic acid having two or more carboxyl groups, such as mono[2-(methyl)propenyloxyethyl] succinate and Mono [2-(methyl)propenyloxyethyl] phthalic acid ester; and mono(meth) acrylate having a carboxyl group and a hydroxyl group polymer at both ends, such as ω-carboxypolycaprolactone (Meth) acrylate.

Among these unsaturated carboxylic acids and unsaturated carboxylic anhydrides, the commercial names of mono(2-propenyloxyethyl) succinate and mono(2-propenyloxyethyl) phthalate are commercially available. They are Light Ester HOA-MS and Light Ester HOA-MPE (Kyoeisha Kagaku Co., Ltd.).

Examples of the aforementioned unsaturated phenol compound include unsaturated phenols such as o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4- Vinyl phenol, o-isopropenyl phenol, m-isopropenyl phenol and p-isopropenyl phenol; and unsaturated naphthol, such as 2-vinyl-1-naphthol, 3-vinyl-1-naphthalene Phenol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol and 3-isopropenyl-1-naphthol.

In the present invention, (meth)acrylic acid and p-vinylphenol are preferred, and (meth)acrylic acid is a particularly preferred acid unsaturated compound.

Examples of the aforementioned alicyclic unsaturated compound include (meth) acrylate such as cyclohexyl (meth) acrylate or (meth) acrylate Ester, (meth) acrylate, tricyclo [5.2.1.0 ^2.6] decan-8-acrylate, (meth) acrylate, tricyclo [5.2.1.0 ^2.6] dec-9-ester, (meth) acrylate, tricyclo [5.2. 1.0 ^2.6 ] indole-3-ene-8-ester, trimethyl [meth)acrylate [5.2.1.0 ^2.6 ]non-3-ene-9-ester, 2-cyclohexyloxyethyl (meth)acrylate, 2-(tricyclo[5.2.1.0 ^2.6 ]癸-8-yloxy)ethyl (meth)acrylate, 2-(tricyclo[5.2.1.0 ^2.6 ]癸-9-yloxy (meth)acrylate Ethyl ester, 2-(tricyclo[5.2.1.0 ^2.6 ]non-3-en-8-yloxy)ethyl (meth)acrylate, 2-(tricyclo[5.2.1.0 ^2.6] ]]-3-ene-9-yloxy)ethyl ester, hexahydrophthalic acid mono[2-(methyl)propenyloxyethyl]ester, hexahydrophthalic acid 1-hydroxyethyl-2 -(Meth)propenyloxyethyl ester, 1-methyl-2-(methyl)propenyloxyethyl hexahydrophthalate and 1-ethyl-2-(methyl) hexahydrophthalate ) propylene methoxyethyl ester; and vinyl ether, such as cyclohexyl vinyl ether, different Vinyl ether, tricyclo[5.2.1.0 ^2.6 ]癸-8-yl vinyl ether, tricyclo[5.2.1.0 ^2.6 ]non-9-yl vinyl ether, tricyclo[5.2.1.0 ^2.6 ]癸-3 -ene-8-yl vinyl ether, tricyclo[5.2.1.0 ^2.6 ]non-3-ene-9-yl vinyl ether, 2-cyclohexyloxyethyl vinyl ether, 2-(tricyclo[5.2 .1.0 ^2.6 ]癸-8-yloxy)ethyl vinyl ether, 2-(tricyclo[5.2.1.0 ^2.6 ]癸-9-yloxy)ethyl vinyl ether, 2-(tricyclo[5.2 .1.0 ^2.6 ]Indol-3-ene-8-yloxy)ethyl vinyl ether, 2-(tricyclo[5.2.1.0 ^2.6 ]non-3-ene-9-yloxy)ethyl vinyl ether , hexahydrophthalic acid mono [2-vinyloxyethyl] ester, hexahydrophthalic acid 1-hydroxyethyl-2-vinyloxyethyl ester, hexahydrophthalic acid 1-methyl-2 - Vinyloxyethyl ester and 1-ethyl-2-vinyloxyethyl hexahydrophthalate.

In the present invention, cyclohexyl (meth)acrylate, (meth)acrylic acid Ester, tricyclo[methyl]acrylic acid [5.2.1.0 ^2.6 ]癸-8-ester, cyclohexyl vinyl ether, different Vinyl ether and tricyclo[5.2.1.0 ^2.6 ]癸-8-ester vinyl ether are preferred, while cyclohexyl (meth)acrylate, trimethyl (meth)acrylate [5.2.1.0 ^2.6 ]癸- 8-ester and (meth)acrylic acid The ester system is a particularly preferred alicyclic unsaturated compound.

The aforementioned alicyclic unsaturated compounds may be used singly or in combination of two or more.

The propylene oxide unsaturated compound is preferably a compound represented by the following formula (1) (hereinafter referred to as "propylene oxide unsaturated compound (1)") or a compound represented by the following formula (2) (hereinafter referred to as "Phenylene oxide unsaturated compound (2)").

(In the formula (1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² , R ³ , R ⁴ And each of R ^{5 is} independently 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 It is an integer from 0 to 6.)

(In the formula (2), R, R ¹ , R ² , R ³ , R ⁴ , R ^S and n are as defined in the above formula (1)).

In the above formulae (1) and (2), examples of the alkyl group having 1 to 4 carbon atoms represented by R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a methyl group and an ethyl group. , n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and tert-butyl.

Examples of the fluoroalkyl group having 1 to 4 carbon atoms represented by R ² , R ³ , R ⁴ and R ⁵ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, 2-fluoroethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, nonafluoro-n-butyl Base, nonafluoro-isobutyl, nonafluoro-t-butyl and nonafluoro-t-butyl.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ² , R ³ , R ⁴ and R ⁵ include a phenyl group, an o-tolyl group, a m-tolyl group and a p-tolyl group.

Examples of the propylene oxide unsaturated compound (1) include (meth) acrylate such as 3-[(meth) propylene methoxymethyl] propylene oxide, 3-[(meth) propylene fluorenyloxy group. Methyl]-2-methyl propylene oxide, 3-[(meth)acryloxymethyl]-3-methyl propylene oxide, 3-[(methyl) propylene methoxymethyl]- 2-ethyl propylene oxide, 3-[(meth)acryloxymethyl]-3-ethyl propylene oxide, 3-[(methyl) propylene methoxymethyl]-2-trifluoro Methyl propylene oxide, 3-[(meth)acryloxymethyl]-2-pentafluoroethyl propylene oxide, 3-[(methyl) propylene methoxymethyl]-2-phenyl Propylene oxide, 3-[(meth)acryloxymethyl]-2,2-difluoroepoxypropane, 3-[(meth)acryloxymethyl]-2,2,4- Trifluoroepoxypropane, 3-[(meth)acryloxymethyl]-2,2,4,4-tetrafluoroepoxypropane, 3-[2-(methyl)propenyloxyethyl ] Propylene oxide, 3-[2-(methyl)acryloxyethyl]-2-methyl propylene oxide, 3-[2-(methyl) propylene methoxyethyl]-3- Propylene oxide, 3-[2-(methyl) propylene oxime Ethylethyl]-2-ethyl propylene oxide, 3-[2-(methyl) propylene methoxyethyl]-3-ethyl propylene oxide, 3-[2-(methyl) propylene oxime Ethylethyl]-2-trifluoromethyl propylene oxide, 3-[2-(methyl) propylene methoxyethyl]-2-pentafluoroethyl propylene oxide, 3-[2-(methyl ) propylene methoxyethyl]-2-phenyl propylene oxide, 3-[2-(methyl) propylene oxyethyl]-2,2-difluoro propylene oxide, 3-[2-( Methyl)propenyloxyethyl]-2,2,4-trifluoroepoxypropane and 3-[2-(methyl)propenyloxyethyl]-2,2,4,4-tetrafluoro Propylene oxide.

Examples of the propylene oxide unsaturated compound (2) include (meth) acrylate such as 2-[(meth) propylene methoxymethyl] propylene oxide, 2-[(meth) propylene fluorenyloxy group. Methyl]-2-methyl propylene oxide, 2-[(meth)acryloxymethyl]-3-methyl propylene oxide, 2-[(meth) propylene methoxymethyl]- 4-methyl propylene oxide, 2-[(meth)acryloxymethyl]-2-ethyl propylene oxide, 2-[(methyl) propylene methoxymethyl]-3-ethyl Propylene oxide, 2-[(meth)acryloxymethyl]-4-ethyl propylene oxide, 2-[(methyl) propylene methoxymethyl]-2-trifluoromethyl epoxide Propane, 2-[(methyl)acryloxymethyl]-3-trifluoromethyl propylene oxide, 2-[(methyl) propylene methoxymethyl]-4-trifluoromethyl epoxide Propane, 2-[(meth)acryloxymethyl]-2-pentafluoroethyl propylene oxide, 2-[(meth)acryloxymethyl]-3-pentafluoroethyl epoxy Propane, 2-[(meth)acryloxymethyl]-4-pentafluoroethyl propylene oxide, 2-[(meth) propylene methoxymethyl]-2-phenyl propylene oxide, 2-[(methyl) Enoxamethoxymethyl]-3-phenylepoxypropane, 2-[(meth)acryloxymethyl]-4-phenylpropene oxide, 2-[(meth)acryloxyloxy Methyl]-2,3-difluoroepoxypropane, 2-[(meth)acryloxymethyl]-2,4-difluoroepoxypropane, 2-[(meth)acryloxyloxy Methyl]-3,3-difluoroepoxypropane, 2-[(meth)acryloxymethyl]-3,4-difluoropropene oxide, 2-[(meth)acryloxyloxy Methyl]-4,4-difluoroepoxypropane, 2-[(meth)acryloxymethyl]-3,3,4-trifluoroepoxypropane, 2-[(meth)acrylofluorene Oxymethyl]-3,4,4 tetrafluoroepoxypropane, 2-[(meth)acryloxymethyl]-3,3,4,4-tetrafluoroepoxypropane, 2-[ 2-(Methyl)propenyloxyethyl]propylene oxide, 2-[2-(methyl)propenyloxyethyl]-2-methyl propylene oxide, 2-[2-(methyl ) propylene methoxyethyl]-3-methyl propylene oxide, 2-[2-(methyl) propylene methoxyethyl]-4-methyl propylene oxide, 2-[2-(methyl ) propylene methoxyethyl]-2-ethyl propylene oxide, 2-[2-(methyl) propylene oxiranyl ethyl] 3-ethyl propylene oxide, 2-[2-(methyl) propylene methoxyethyl]-4-ethyl propylene oxide, 2-[2-(methyl) propylene methoxyethyl]- 2-trifluoromethyl propylene oxide, 2-[2-(methyl) propylene methoxyethyl]-3-trifluoromethyl propylene oxide, 2-[2-(methyl) propylene oxy group Ethyl]-4-trifluoromethyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-2-pentafluoroethyl propylene oxide, 2-[2-(methyl) Propylene methoxyethyl]-3-pentafluoroethyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-4-pentafluoroethyl propylene oxide, 2-[2- (Meth) propylene methoxyethyl]-2-phenyl propylene oxide, 2-[2-(methyl) propylene methoxyethyl]-3-phenyl propylene oxide, 2-[2- (Meth) propylene methoxyethyl]-4-phenyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-2,3-difluoro propylene oxide, 2-[ 2-(Methyl)propenyloxyethyl]-2,4-difluoroepoxypropane, 2-[2-(methyl)propenyloxyethyl]-3,3-difluoropropene oxide ,2-[2-(methyl)acryloxyethyl]-3,4-difluoroepoxy Alkane, 2-[2-(methyl)propenyloxyethyl]-4,4-difluoroepoxypropane, 2-[2-(methyl)propenyloxyethyl]-3,3, 4-trifluoroepoxypropane, 2-[2-(methyl)propenyloxyethyl]-3,4,4-trifluoroepoxypropane and 2-[2-(methyl)propenyloxyl Ethyl]-3,3,4,4-tetrafluoropropylene oxide.

In the propylene oxide unsaturated compound (1) and the propylene oxide unsaturated compound (2), 3-[(meth)acryloxymethylmethyl propylene oxide, 3-[(methyl) ) propylene methoxymethyl]-3-ethyl propylene oxide, 3-[(methyl) propylene methoxymethyl]-2-trifluoromethyl propylene oxide, 3-[(meth) propylene醯oxymethyl]-2-phenyl propylene oxide, 2-[(meth) propylene methoxymethyl] propylene oxide and 2-[(meth) propylene methoxymethyl]-4- Trifluoromethyl propylene oxide is preferred, and 3-(methacryloxymethyl) propylene oxide, 3-(methacryloxymethyl)-3-ethyl propylene oxide, 3- (Methethyloxymethyl)-2-trifluoromethyl propylene oxide, 3-(methacryloxymethyl)-2-phenyl propylene oxide, 2-(methacryl oxime) Methyl) propylene oxide and 2-(methacryloxymethyl)-4-trifluoromethyl propylene oxide are particularly preferred because the resulting radiation-sensitive composition has a wide development tolerance and is obtained. The chemical resistance of the color layer is improved.

In the present invention, a (propylene oxide alkyl) ether of a vinyl phenol such as (3-epoxypropenylmethoxy)-p-vinylbenzene or [2-(3-epoxypropane) ethoxylate And p-vinylbenzene, (2-epoxypropenylmethoxy)-p-vinylbenzene and [2-(2-epoxypropenyl)ethoxy]-p-vinylbenzene; (propylene oxide alkyl) vinyl ether, such as (3-epoxypropanemethyl)vinyl ether, [2-(3-epoxypropenyl)ethyl]vinyl ether, (2-epoxy Propyl methyl)vinyl ether and [2-(2-epoxypropenyl)ethyl vinyl ether can also be used as the propylene oxide unsaturated compound (1) and the propylene oxide unsaturated compound (2). A propylene oxide unsaturated compound.

The aforementioned propylene oxide unsaturated compounds may be used singly or in combination of two or more.

The copolymer (B1) may additionally contain, as a basic component, an unsaturated compound other than an acid unsaturated compound, an alicyclic unsaturated compound, and a propylene oxide unsaturated compound (hereinafter referred to as "another unsaturated compound").

Examples of other unsaturated compounds include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, ortho- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; hydrazine, such as hydrazine and 1-methyl hydrazine; unsaturated hydrazine Amines such as maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, econazole, and citraconin; unsaturated carboxylic acid Acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (methyl) ) isobutyl acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (methyl) ) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy butyl (meth) acrylate Ester, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( 2-phenoxyethyl methacrylate, methoxybisethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate , methoxybispropanediol (meth) acrylate, (meth) acrylate Ester, dicyclopentadienyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and glycerol mono(meth)acrylate; unsaturated alkyl amide of carboxylic acid, such as 2-Aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylamine (meth)acrylate Propyl propyl ester, 3-aminopropyl (meth) acrylate and 3-dimethylaminopropyl (meth) acrylate; unsaturated glycidyl carboxylate such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated decylamines such as (meth) acrylamide, α-chloropropenylamine and N-2-hydroxyl Ethyl (meth) acrylamide; vinyl carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl Ether and allyl glycidyl ether; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and having a single at the end of the polymer molecular chain ( Macromonomers yl) Bing Xixi the group, such as polystyrene, poly (meth) acrylate, poly - (meth) acrylate, n-butyl, and poly silicon oxide.

These other unsaturated compounds may be used singly or in combination of two or more.

In the present invention, the copolymer (BI) is preferably a copolymer comprising (b1), (b2) and (b3) as a basic component and, as the case may be, (b4) (hereinafter referred to as "copolymer (BII)" And wherein (b1) is at least one acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is at least one selected from the group consisting of cyclohexyl (meth)acrylate and (meth)acrylic acid. An ester and an alicyclic unsaturated compound of a tricyclo[5.2.1.0 ^2.6 ]癸-8-ester of (meth)acrylic acid, and (b3) is at least one selected from the group consisting of 3-(methacryloxymethyl) ring Oxypropane, 3-(methacryloxymethyl)-3-ethyl propylene oxide, 3-(methacryloxymethyl)-2-trifluoromethyl propylene oxide, 3-( Methyl propylene methoxymethyl)-2-phenyl propylene oxide, 2-(methacryloxymethyl) propylene oxide and 2-(methacryloxymethyl)-4-tri a propylene oxide unsaturated compound of fluoromethyl propylene oxide, and (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, Methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, mono(meth)acrylate, polystyrene And other unsaturated compounds of polymethyl methacrylate macromonomer.

In particular, the copolymer (BII) is, for example, a copolymer (BII-1) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) Is an acid unsaturated compound consisting essentially of (meth)acrylic acid, (b2) is an alicyclic unsaturated compound consisting essentially of cyclohexyl (meth)acrylate, and (b3) is substantially a propylene oxide unsaturated compound composed of 3-[(meth)acryloxymethyl] propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene and N-cyclohexyl-n-butene Yttrium, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate Ester, glycerol mono(meth) acrylate, polystyrene macromonomer and other unsaturated compounds of polymethyl methacrylate macromonomer; containing (b1), (b2) and (b3) as basic components and The copolymer (BII-2) according to the case (b4), wherein the (b1) is an acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is substantially composed of a (meth)acrylic acid ring. Alicyclic ring composed of hexyl ester An unsaturated compound, and (b3) is a propylene oxide unsaturated compound consisting essentially of 3-[(meth)acryloxymethyl]-3-ethyl propylene oxide, and optionally (b4) Is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Other unsaturated compounds of esters, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomers and polymethyl methacrylate macromonomers; a copolymer (BII-3) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is an acid consisting essentially of (meth)acrylic acid An unsaturated compound, (b2) is an alicyclic unsaturated compound consisting essentially of cyclohexyl (meth)acrylate, and (b3) is substantially 3-[(meth)acryloxymethylmethyl a propylene oxide unsaturated compound composed of 2-trifluoromethyl propylene oxide, and the case where (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N- Phenyl Maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(methyl) Other unsaturated compounds of acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer; copolymers containing (b1), (b2) and (b3) as basic components and optionally (b4) (BII-4), wherein (b1) is an acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is an alicyclic group consisting essentially of cyclohexyl (meth)acrylate An unsaturated compound, and (b3) is a propylene oxide unsaturated compound consisting essentially of 3-[(methyl)acryloxymethyl]-2-phenyl propylene oxide, and optionally (b4) Is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Ester, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and other unsaturated compounds of polymethyl methacrylate macromonomer a copolymer (BII-5) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is an acid consisting essentially of (meth)acrylic acid An unsaturated compound, (b2) is an alicyclic unsaturated compound consisting essentially of cyclohexyl (meth) acrylate, and (b3) is substantially 2-[(meth) propylene methoxymethyl a propylene oxide unsaturated compound composed of propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenylbutylene Imine, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, poly benzene Other unsaturated compounds of ethylene macromonomer and polymethyl methacrylate macromonomer; copolymers containing (b1), (b2) and (b3) as basic components and optionally (b4) (BII-6) Wherein (b1) is an acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is an alicyclic unsaturated compound consisting essentially of cyclohexyl (meth)acrylate, and (b3) is basic a propylene oxide unsaturated compound consisting of 2-[(methyl)acryloxymethyl]-4-trifluoromethyl propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene , N-cyclohexyl maleimide, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid Other unsaturated compounds of propyl ester, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer; (b1), (b2) And (b3) a copolymer (BII-7) as a basic component and optionally (b4), wherein the (b1) is an acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is Basically (meth)acrylic acid An alicyclic unsaturated compound composed of an ester, and (b3) is a propylene oxide unsaturated compound consisting essentially of 3-[(meth) propylene methoxymethyl] propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, and (meth)acrylic acid 2- Other unsaturateds of hydroxyethyl ester, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(meth)acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer a compound (B1-8) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) consists essentially of (meth)acrylic acid. Acid-unsaturated compound, (b2) is substantially composed of (meth)acrylic acid An alicyclic unsaturated compound composed of an ester, and (b3) is a propylene oxide unsaturated compound consisting essentially of 3-[(meth)acryloxymethyl]-3-ethyl propylene oxide, And optionally, (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, (A) 2-hydroxyethyl acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate giant Other unsaturated compounds of the body; comprising (b1), (b2) and (b3) as a basic component and optionally (b4) a copolymer (BII-9), wherein the (b1) is substantially An acid unsaturated compound composed of acrylic acid, (b2) is substantially composed of (meth)acrylic acid An alicyclic unsaturated compound composed of an ester, and (b3) is an propylene oxide unsaturated substantially consisting of 3-[(meth)acryloxymethyl]-2-trifluoromethyl propylene oxide The compound, and optionally (b4), is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(meth)acrylate, polystyrene macromonomer and polymethyl methacrylate Other unsaturated compounds of macromonomer; copolymers (BII-10) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is substantially An acid unsaturated compound composed of (meth)acrylic acid, (b2) is substantially composed of (meth)acrylic acid An alicyclic unsaturated compound composed of an ester, and (b3) is a propylene oxide unsaturated compound consisting essentially of 3-[(meth)acryloxymethyl]-2-phenyl propylene oxide, And optionally, (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, (A) 2-hydroxyethyl acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate giant Other unsaturated compounds of the body; copolymers (BII-11) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is substantially An acid unsaturated compound composed of acrylic acid, (b2) is substantially composed of (meth)acrylic acid An alicyclic unsaturated compound composed of an ester, and (b3) is a propylene oxide unsaturated compound consisting essentially of 2-[(meth) propylene methoxymethyl] propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, and (meth)acrylic acid 2- Other unsaturateds of hydroxyethyl ester, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(meth)acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer a compound comprising (b1), (b2) and (b3) as a basic component and optionally (b4) a copolymer (BII-12) wherein the (b1) consists essentially of (meth)acrylic acid. An acid unsaturated compound, (b2) is substantially composed of (meth)acrylic acid An alicyclic unsaturated compound composed of an ester, and (b3) is an propylene oxide unsaturated substantially consisting of 2-[(meth)acryloxymethyl]-4-trifluoromethyl propylene oxide a compound, and optionally (b4), is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(meth)acrylate, polystyrene macromonomer and polymethyl methacrylate Other unsaturated compounds of macromonomer; copolymers (BII-13) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is substantially (meth) acrylic acid, consisting of an unsaturated compound, (b2) consisting essentially of (meth) acrylate, tricyclo [5.2.1.0 ^2.6] dec-8 consisting of cycloaliphatic esters of unsaturated compound, and ( B3) is a propylene oxide unsaturated compound consisting essentially of 3-[(meth) propylene methoxymethyl] propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene, N- Cyclohexyl Maleimide, N-phenylmaleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (A) Other unsaturated compounds of benzyl acrylate, glycerol mono(meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer; containing (b1), (b2) and (b3) as a basic component and, as the case may be (b4) a copolymer (BII-14), wherein (b1) is an acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is substantially An alicyclic unsaturated compound composed of a tricyclo[5.2.1.0 ^2.6 ]癸-8-ester of acrylic acid, and (b3) is substantially composed of 3-[(meth)acryloxymethyl]-3 a propylene oxide unsaturated compound composed of ethyl propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl-n-butylene Diquinone imine, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(meth)acrylate, Polystyrene giant monomer and Other unsaturated compounds of methyl methacrylate macromonomer; copolymers (BII-15) comprising (b1), (b2) and (b3) as basic components and optionally (b4), wherein (b1 ) consisting essentially of (meth) acrylic acid, consisting of an unsaturated compound, (b2) consisting essentially of a cycloaliphatic (meth) acrylate, tricyclo [5.2.1.0 ^2.6] dec-8 are not esters consisting of a saturated compound, and (b3) is a propylene oxide unsaturated compound consisting essentially of 3-[(meth)acryloxymethyl]-2-trifluoromethyl propylene oxide, and optionally B4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and other unsaturated compounds of polymethyl methacrylate macromonomer a copolymer (BII-16) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is substantially composed of (meth)acrylic acid Acid unsaturated compound (b2) consisting essentially of (meth) acrylate, tricyclo [5.2.1.0 ^2.6] dec-8 consisting of cycloaliphatic esters of unsaturated compound, and (b3) consisting essentially of 3 - [(methylamino) a propylene oxide unsaturated compound composed of propylene methoxymethyl]-2-phenyl propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene and N-cyclohexyl-n-butylene Amine, N-phenyl maleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, Other unsaturated compounds of glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer; containing (b1), (b2) and (b3) as basic components and optionally The copolymer (BII-17) of (b4), wherein (b1) is an acid unsaturated compound consisting essentially of (meth)acrylic acid, and (b2) is substantially tricyclic (meth)acrylic acid [ 5.2.1.0 ^2.6 ] an alicyclic unsaturated compound composed of an oxime-8-ester, and (b3) a propylene oxide consisting essentially of 2-[(meth) propylene methoxymethyl] propylene oxide Unsaturated compound, and as appropriate The (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenyl maleimide, methyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer An unsaturated compound; a copolymer (BII-18) comprising (b1), (b2) and (b3) as a basic component and optionally (b4), wherein the (b1) is substantially composed of (meth)acrylic acid The acid-unsaturated compound composed of (b2) is an alicyclic unsaturated compound consisting essentially of tricyclo[5.2.1.0 ^2.6 ]癸-8-ester (meth)acrylate, and (b3) is substantially a propylene oxide unsaturated compound consisting of 2-[(meth)acryloxymethyl]-4-trifluoromethyl propylene oxide, and optionally (b4) is at least one selected from the group consisting of styrene, N-cyclohexylmethyleneimine, N-phenylmaleimide, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate Ester, (meth)acrylic acid Other unsaturated compounds of benzyl ester, glycerol mono(meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer.

Among these copolymers (BII), copolymer (BII-1), copolymer (BII-2), copolymer (BII-7), copolymer (BII-8), copolymer (BII-13) and copolymerization The substance (BII-14) is preferred.

In the copolymer (BI), the copolymerization amount of the acid-unsaturated compound is preferably from 1 to 40% by weight, particularly preferably from 5 to 30% by weight, based on the copolymer, and the copolymerization amount of the alicyclic unsaturated compound is preferably copolymer. It is 1 to 50% by weight, particularly preferably 1 to 30% by weight, and the copolymerization amount of the propylene oxide unsaturated compound is preferably from 1 to 60% by weight, particularly preferably from 10 to 45% by weight, based on the copolymer, and the other is not The copolymerization amount of the saturated compound is preferably from 0 to 50% by weight, more preferably from 1 to 50% by weight, particularly preferably from 5 to 40% by weight, based on the copolymer.

In the present invention, when the copolymerization amount of the unsaturated compound contained in the copolymer (BI) is set within the above range, the storage stability of the alkali-soluble resin itself and the storage stability of the pigment dispersion and the liquid composition can be obtained. A radiation-sensitive composition that is excellent and has high sensitivity, solvent resistance, and adhesion to a substrate, even if the pigment content is high.

In the present invention, other alkali-soluble resins may be used in combination with the copolymer (BI).

The other alkali-soluble resin described above is not particularly limited as long as it has solubility as a binder of the colorant (A) and in the alkali developer used in the development step for forming the coloring layer. For example, it is preferably an alkali-soluble resin having a carboxyl group. Examples of other carboxyl group-containing alkali-soluble resins are at least one of the unsaturated carboxylic acids exemplified in the copolymer (BI) and at least one alicyclic unsaturated compound and other unsaturated compounds selected from the group consisting of copolymers (BI). Copolymer.

Preferred examples of other alkali-soluble resins are copolymers of (i) a carboxyl group-containing unsaturated compound consisting essentially of (meth)acrylic acid and (ii) at least one selected from the group consisting of styrene and N-phenyl cis. Butyleneimine, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, glycerol mono(meth)acrylic acid Ester, polystyrene macromonomer and polymethyl methacrylate macromonomer.

In the present invention, the weight average molecular weight (hereinafter referred to as "Mw") of the copolymer (BI) and other alkali-soluble resins measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran) in terms of polystyrene is preferably each. It is 2,000 to 300,000, more preferably 3,000 to 100,000.

The number average molecular weight (hereinafter referred to as "Mn") of the copolymer (BI) and other alkali-soluble resins measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran) in terms of polystyrene is preferably 1,000 to 1,000 60,000, more preferably 2,000 to 25,000.

In the present invention, radiation sensitivity with excellent developability is obtained by using the combination of the above-mentioned copolymer (BI) or copolymer (BI) having a specific Mw and Mn and the aforementioned other alkali-soluble resin having a specific Mw and Mn. Sexual composition. Therefore, a pixel having a sharp pattern edge and a black matrix can be formed, and it is difficult to cause residue, contamination or film residue on the substrate or the light shielding layer of the unexposed portion during development.

The Mw/Mn ratio of the copolymer (BI) and other alkali-soluble resins is preferably from 1 to 5, more preferably from 1 to 4.

In the present invention, the copolymer (BI) may be used singly or in combination of two or more. Other alkali-soluble resins may be used singly or in combination of two or more.

In the present invention, the total amount of the alkali-soluble resin is preferably from 10 to 1,000 parts by weight, more preferably from 20 to 500 parts by weight, per 100 parts by weight of the coloring agent (A). When the total amount of the alkali-soluble resin is less than 10 parts by weight, alkali developability may be lowered, or contamination or film residue may be generated on the substrate or the light-shielding layer of the unexposed portion. When the total amount is more than 1,000 parts by weight, the concentration of the colorant becomes relatively low, and it may be difficult to achieve the target color density of the film.

The amount of the copolymer (BI) in the alkali-soluble resin is preferably from 10 to 100% by weight, more preferably from 20 to 100% by weight. When the amount of the copolymer (BI) is less than 10% by weight, the effects to be achieved by the present invention may be impaired.

- (C) Polyfunctional Monomer - The polyfunctional single system of the present invention is a monomer having two or more polymerizable unsaturated bonds.

Examples of the polyfunctional monomer include alkanediols such as di(meth)acrylates of ethylene glycol and propylene glycol; polyalkylene glycols such as di(meth)acrylates of polyethylene glycol and polypropylene glycol; a poly(meth)acrylate having a polyhydric alcohol having 3 or more hydroxyl groups and a dicarboxylic acid-modified product thereof such as glycerin, trimethylolpropane, pentaerythritol, and diisopentaerythritol; a methyl acrylate such as a polyester, an epoxy resin, a urethane resin, an alkyd resin, a polyoxyl resin, and a spiro resin; a polymer having a hydroxyl group at both ends, such as a hydroxyl group at both ends Poly-1,3-butadiene, polyisoprene with hydroxyl groups at both ends, and di(meth)acrylate of polycaprolactone having hydroxyl groups at both ends; and phosphoric acid three [2] - (Meth) propylene oxiranyl ethyl ester.

Among these polyfunctional monomers, polyhydric alcohols having 3 or more hydroxyl groups and poly(meth)acrylates thereof modified by dicarboxylic acid are preferred, and examples thereof include trimethylolpropane triacrylate. Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, diisoamyl Tetraol pentaacrylate, diisopentyl alcohol pentamethacrylate, diisopentyl alcohol hexaacrylate, diisopentyl alcohol hexamethacrylate, and represented by the following formulas (3) and (4) Compound.

Among these compounds, trimethylolpropane triacrylate, pentaerythritol triacrylate and diisopentyl alcohol hexaacrylate are particularly preferred because they provide excellent strength and surface smoothness, and are extremely less than unexposed. A colored layer of contaminated or film residue is formed on a portion of the substrate or light-shielding layer.

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

The amount of the polyfunctional monomer of the present invention is preferably 5 to 5 parts by weight, more preferably 20 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin (B). When the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer may be lowered, and when the amount is more than 500 parts by weight, the alkali developability may be lowered, or the basis of the unexposed portion may be lowered. Contamination or film residue may form on the material or on the light-shielding layer.

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

Examples of the aforementioned monofunctional monomer include a compound represented by the acid-unsaturated compound, an alicyclic unsaturated compound or other unsaturated compound in the aforementioned alkali-soluble resin (B), and N-(meth)acryl fluorenyl group. Morpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and commercially available M-5600 (trade name of Toagosei Chemical Industry Co., Ltd.).

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

The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin (B). When the total amount is less than 5 parts by weight, the strength and surface smoothness of the colored layer may be lowered, and when the total amount is more than 500 parts by weight, alkali developability may be lowered, or the unexposed portion of the substrate or the light shielding layer may be Produces stains or film residues.

- (D) Photopolymerization initiator - The photopolymerization initiator of the present invention is a compound which forms an active material upon exposure to visible radiation, ultraviolet radiation, far ultraviolet radiation, electron radiation or X-ray radiation, and the active material can The polymerization of the aforementioned polyfunctional monomer (C) and optionally a monofunctional monomer is initiated.

The photopolymerization initiator is, for example, a compound based on acetal benzene, a compound based on biimidazole, and three a compound of benzoin as a substrate, a compound of benzophenone as a substrate, a compound of α-diketone as a substrate, a compound of polycyclic oxime as a substrate, and a ketone ketone. a compound of the substrate, a compound having a diazo group as a substrate, a compound having an O-mercaptopurine as a substrate, a compound having a sulfonium salt as a substrate or a substrate having a quinone imine sulfonate group as a substrate. Compound. These compounds form active free radicals, active acids or both upon exposure.

In the present invention, the aforementioned photopolymerization initiators may be used singly or in combination of two or more. Preferably, at least one compound selected from the group consisting of acetaminobenzene as a substrate and biimidazole as a substrate is used. As the substrate of the present invention, a compound which is a substrate and a compound which is based on O-mercaptopurine is used as the photopolymerization initiator of the present invention.

In the present invention, the amount of the photopolymerization initiator is preferably 0.01 to 120 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer (C) or the polyfunctional monomer and the monofunctional monomer. More preferably 1 to 100 parts by weight. When the amount of the photopolymerization initiator is less than 0.01 parts by weight, it may be difficult to obtain a filter having a predetermined coloring pattern because the curing by exposure is incomplete, and when the amount is more than 120 parts by weight The formed color layer may be detached from the substrate during development.

Examples of the compound of the phthalylbenzene-based substrate in the preferred photopolymerization initiator of the present invention include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1. -[4-(Methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane 1-ketone, 1-hydroxycyclohexyl. Phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one and 1,2-octanedione.

Among these ethoxylated benzene compounds, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine The base-1-(4-morpholinylphenyl)butan-1-one and 1,2-octanedione are preferred.

The aforementioned compounds based on ethenylbenzene may be used singly or in combination of two or more.

When a compound based on acetal benzene is used as the photopolymerization initiator of the present invention, the amount of the ethyl benzene-based compound is 100 parts by weight of the polyfunctional monomer (C) or polyfunctional. The total amount of the monomer and the monofunctional monomer is preferably from 0.01 to 80 parts by weight, more preferably from 1 to 60 parts by weight, particularly preferably from 1 to 30 parts by weight. When the amount of the acetal-based benzene-based compound is less than 0.01 part by weight, it may be difficult to obtain a filter having a predetermined chromatic pattern due to incomplete curing by exposure. When the amount is more than 80 parts by weight, the formed coloring layer may be detached from the substrate during development.

Examples of the aforementioned biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1. 2'-Biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole, 2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole, 2 , 2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole and 2,2'-bis(2,4,6- Tribromophenyl)-4,4',5,5'-tetraphenyl 1,2'-biimidazole.

Among these compounds which are based on 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 and 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis(2,4-dichlorophenyl)-4,4' , 5,5'-tetraphenyl-1,2'-biimidazole is preferred.

These biimidazole-based compounds have excellent solubility in a solvent, do not form foreign substances, such as undissolved products and precipitates, are highly sensitive, and sufficiently promote the curing reaction by low-energy exposure. It does not cause a curing reaction in the unexposed portion. Therefore, the coating film obtained after the exposure is clearly distinguished into a solidified portion which is insoluble in the developer and an uncured portion which has high solubility in the developer, and can form a filter having a predetermined coloring layer pattern having high definition without side etching. Light film.

The aforementioned biimidazole-based compounds may be used singly or in combination of two or more.

When a diimidazole-based compound is used as the photopolymerization initiator of the present invention, the amount of the biimidazole-based compound is 100 parts by weight of the polyfunctional monomer (C) or the polyfunctional monomer and The total amount of the monofunctional monomer is preferably from 0.01 to 40 parts by weight, more preferably from 1 to 30 parts by weight, particularly preferably from 1 to 20 parts by weight. When the amount of the biimidazole-based compound is less than 0.01 parts by weight, it may be difficult to obtain a filter having a predetermined color layer pattern because the curing by exposure is incomplete. When the amount is more than 40 parts by weight, the formed coloring layer may be peeled off from the substrate, and the film surface of the colored layer may become rough during development.

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

The term "hydrogen donor" as used in the present invention means a compound which can provide a hydrogen atom to a radical formed by the biimidazole-based compound upon exposure.

The hydrogen donor of the present invention is preferably a thiol-based compound or an amine-based compound as defined below.

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

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

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

These hydrogen donors are described in detail below.

The thiol-based hydrogen donor may have at least one benzene ring or heterocyclic ring or both. When it has two or more of such rings, a fused ring can be formed.

When the thiol-based hydrogen donor has two or more thiol groups, at least one of the other thio groups may be alkyl, aralkyl or aryl as long as at least one free thiol group is retained. Substituted by the base. Further, as long as at least one free thiol group is retained, the thiol-based hydrogen donor may have a structural unit in which two sulfur atoms are bonded via a divalent organic group (such as an alkylene group) or two of them A structural unit in which an atom is bonded in the form of a disulfide.

Further, the thiol-based hydrogen donor may be substituted at a position other than the thiol group (etc.) by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, Substituted phenoxycarbonyl or nitrile group.

Examples of such thiol-based hydrogen donors include 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2,5-dihydrogen. Thio-1,3,4-thiadiazole and 2-hydrothio-2,5-dimethylaminopyridine.

Among these hydrogen donors having a thiol as a substrate, 2-hydrothiobenzothiazole and 2-hydrothiobenzoxazole are preferred, and 2-hydrothiobenzothiazole is particularly preferred.

The amine-based hydrogen donor may have at least one benzene ring or heterocyclic ring or both. When it has two or more of such rings, a fused ring can be formed.

At least one amine group of the amine-based hydrogen donor may be substituted with an alkyl or substituted alkyl group. The amine-based hydrogen donor may be substituted at a position other than the amine group (etc.) by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, or a substituted group. Phenoxycarbonyl or nitrile group.

Examples of the aforementioned amine-based hydrogen donor include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoethenylbenzene, 4-dimethylaminopropyl phenyl benzene, ethyl-4-dimethylamino benzoate, 4-dimethylaminobenzoic acid and 4 - Dimethylaminobenzonitrile.

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

The amine-based hydrogen supply system is used as a sensitizer even when a photopolymerization initiator other than a compound in which biimidazole is used as a substrate is used.

In the present invention, the aforementioned hydrogen donors may be used singly or in combination of two or more. It is preferred to use at least one thiol-based hydrogen donor in combination with at least one amine-based hydrogen donor because the formed coloring layer hardly falls off from the substrate during development and has a high Strength and sensitivity.

Preferred examples of the combination of the thiol-based hydrogen donor and the amine-based hydrogen donor include 2-hydrothiobenzothiazole and 4,4'-bis(dimethylamine). a combination of benzophenone, a combination of 2-hydrothiobenzothiazole and 4,4'-bis(diethylamino)benzophenone, 2-hydrothiobenzoxazole and 4, A combination of 4'-bis(dimethylamino)benzophenone and a combination of 2-hydrothiobenzoxazole and 4,4'-bis(diethylamino)benzophenone. Combination of 2-hydrothiobenzothiazole with 4,4'-bis(diethylamino)benzophenone and 2-hydrothiobenzoxazole with 4,4'-double in these combinations The combination of (diethylamino)benzophenone is preferred, and the combination of 2-hydrothiobenzothiazole and 4,4'-bis(diethylamino)benzophenone is particularly preferred.

Comparison of the weight of a thiol-based hydrogen donor relative to an amine-based hydrogen donor in a combination of a thiol-based hydrogen donor and an amine-based hydrogen donor The best is 1:1 to 1:4, more preferably 1:1 to 1:3.

When the hydrogen donor is used in combination with the biimidazole-based compound of the present invention, the hydrogen donor is present in an amount of 100 parts by weight of the polyfunctional monomer (C) or the polyfunctional monomer and the monofunctional monomer. The total amount is preferably from 0.01 to 40 parts by weight, more preferably from 1 to 30 parts by weight, particularly preferably from 1 to 20 parts by weight. When the amount of the hydrogen donor is less than 0.01 parts by weight, the effect of improving sensitivity may be lowered. When the amount is more than 40 parts by weight, the formed coloring layer may be detached from the substrate during development.

The aforementioned three Examples of compounds that are substrates include those having a halomethyl group a compound that is a substrate, such as 2,4,6-tris(trichloromethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three And 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s .

These three 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-three in the substrate Very good.

The aforementioned three The compounds which are the substrate may be used singly or in combination of two or more.

Use this to three When the compound which is a substrate is used as the photopolymerization initiator of the present invention, the The amount of the compound which is a substrate is preferably 0.01 to 40 parts by weight, more preferably 1 to 30, based on 100 parts by weight of the total of the polyfunctional monomer (C) or the polyfunctional monomer and the monofunctional monomer. The parts by weight are particularly preferably 1 to 20 parts by weight. When the three When the amount of the compound as the substrate is less than 0.01 part by weight, it may be difficult to obtain a filter having a predetermined coloring layer pattern because the curing by exposure is incomplete. When the amount is more than 40 parts by weight, the formed coloring layer may be detached from the substrate during development.

Examples of the aforementioned compound having O-mercaptopurine as a substrate include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzidine), 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzylhydrazine), 1-[4-(benzylidene)phenyl]-octane -1,2-diketone 2-(O-benzidine), 1-[9-ethyl-6-(2-methylbenzylidene)-9.H.-carbazol-3-yl]B Ketone 1-(O-acetamidine), 1-[9-ethyl-6-(3-methylbenzylindenyl)-9.H.-oxazol-3-yl]ethanone 1-(O- Ethylene) and 1-[9-ethyl-6-benzylindol-9.H.-oxazol-3-yl]-ethanone 1-(O-acetamidine).

Among the compounds based on O-mercaptopurine, 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzidine) and 1 -[9-Ethyl-6(2-methylindenyl)-9.H.-oxazol-3-yl]ethanone 1-(O-acetamidine) is particularly preferred.

The aforementioned O-mercaptopurine-based compounds may be used singly or in combination of two or more.

When a compound having O-mercaptopurine as a substrate is used as the photopolymerization initiator of the present invention, the amount of the compound having O-mercaptopurine as a substrate is 100 parts by weight of the polyfunctional monomer (C) or The total amount of the polyfunctional monomer and the monofunctional monomer is preferably from 0.01 to 40 parts by weight, more preferably from 1 to 30 parts by weight, particularly preferably from 1 to 20 parts by weight. When the amount of the O-acetyl compound is less than 0.01 parts by weight, it may be difficult to obtain a filter having a predetermined coloring layer pattern because curing by exposure is incomplete. When the amount is more than 40 parts by weight, the formed coloring layer may be detached from the substrate during development.

The aforementioned compound having a sulfonium salt as a substrate is, for example, a diaryliodonium salt, a triarylsulfonium salt or a diarylphosphonium salt.

Examples of the aforementioned diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, Diphenyl iodonium trifluoroacetate, diphenyl iodonium p-toluenesulfonate, 4-methoxyphenyl phenyl iodonium tetrafluoroborate, 4-methoxyphenyl phenyl iodonium hexafluorophosphate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, p- 4-methoxyphenylphenyliodonium tosylate, bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(4-t-butylphenyl)iodonium hexafluoroarsenate, Bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoroacetate and bis(4-t-butylbenzene)-p-toluenesulfonate Base) iodine.

Examples of the aforementioned triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, and three Triphenylsulfonium fluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphate , 4-methoxyphenyl diphenyl sulfonium hexafluoroarsenate, 4-methoxyphenyl diphenyl sulfonium trifluoromethanesulfonate, 4-methoxyphenyl diphenyl sulphate Bismuth, p-toluenesulfonic acid 4-methoxyphenyldiphenylsulfonium sulfonate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphate Thiopurine, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenyl p-toluenesulfonic acid Thiophenyl diphenyl sulfonium and 4-phenylthiophenyl diphenyl sulfonium p-toluenesulfonate.

Examples of the aforementioned diarylphosphonium salt include hexafluorophosphonic acid (1-6-η-cumene) ( η -cyclopentadienyl) iron.

Among the compounds having a sulfonium salt as a substrate, diphenyliodonium hexafluorophosphonate and triphenylsulfonium trifluoromethanesulfonate are particularly preferred. The aforementioned compounds having a sulfonium salt as a substrate may be used singly or in combination of two or more.

When a sulfonium salt-based compound is used as the photopolymerization initiator of the present invention, the amount of the sulfonium salt-based compound is 100 parts by weight of the polyfunctional monomer (C) or the polyfunctional monomer and The total amount of the monofunctional monomer is preferably from 0.01 to 40 parts by weight, more preferably from 1 to 30 parts by weight, particularly preferably from 1 to 20 parts by weight. When the amount of the compound based on the onium salt is less than 0.01 part by weight, it may be difficult to obtain a filter having a predetermined coloring layer pattern because the curing by exposure is incomplete. When the amount is more than 40 parts by weight, the formed coloring layer may be detached from the substrate during development.

- Additives - The radiation-sensitive composition used to form the colored layer of the present invention may optionally contain various additives.

The aforementioned additives include organic acids, organic amine based compounds (excluding the aforementioned hydrogen donors), curing agents, and curing assistants.

The aforementioned organic acid and organic amine based compound are used to further improve the solubility of the radiation-sensitive composition in an alkali developer and further suppress the generation of insoluble products remaining after development.

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

Examples of the aforementioned aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; dicarboxylic acids such as oxalic acid. , malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, azelaic acid, basic acid, methylmalonic acid, ethylmalonic acid, dimethyl Malonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, isaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; and tricarboxylic acid Such as glycerol tricarboxylic acid, aconitic acid and camphorone acid.

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

Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, lauric acid, benzotricarboxylic acid, and dimethylbenzoic acid; aromatic dicarboxylic acids such as phthalic acid, Isophthalic acid and terephthalic acid; aromatic polycarboxylic acids having 3 or more carboxyl groups, such as trimellitic acid, trimellitic acid, pyromellitic acid and pyromellitic acid; and phenylacetic acid, hydrogenated Oleic acid, hydrogenated cinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamic acid, coumaric acid and umbrella acid.

Among these organic acids, aliphatic dicarboxylic acids are used in view of alkali solubility, solubility in a solvent described below, and prevention of contamination and film residue on a substrate or a light-shielding layer of an unexposed portion. Preferably, malonic acid, adipic acid, isaconic acid, citraconic acid, fumaric acid and mesaconic acid are particularly preferred aliphatic carboxylic acids. The aromatic dicarboxylic acid is preferred, and the phthalic acid is a particularly preferred phenylcarboxylic acid.

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

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

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

Examples of the aforementioned aliphatic amines include mono(cyclo)alkylamines such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, positive Amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methyl Cyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, and 4-ethylcyclohexylamine; di(cyclo)alkyl An amine such as a methyl group. Ethylamine, diethylamine, methyl. N-propylamine, ethyl. N-propylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, di-secondbutylamine, di-t-butylamine, two - n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine; tri(cyclo)alkylamines such as dimethyl. Ethylamine, methyl. Diethylamine, triethylamine, dimethyl. N-propylamine, diethyl. N-propylamine, methyl. Di-n-propylamine, ethyl. Di-n-propylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-tert-butylamine, tri-tert-butylamine , tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, and tricyclohexylamine; Alkanolamines, such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentane Alcohol, 6-amino-1-hexanol and 4-amino-1-cyclohexanol; di(cyclo)alkanolamines, such as diethanolamine, di-n-propanolamine, di-isopropanolamine, two - n-butanolamine, di-isobutanolamine, di-n-pentanolamine, di-n-hexanolamine and bis(4-cyclohexanol)amine; tri(cyclo)alkanolamines, such as triethanolamine, tri- N-propanolamine, tri-isopropanolamine, tri-n-butanolamine, tri-isobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine and tris(4-cyclohexanol)amine; amine Alkane (cyclo)alkane, such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amine -1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexane Alkanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propane Alcohol and 2-diethylamino-1,3-propanediol; amine-containing cycloalkane methanol, such as 1-aminocyclopentane methanol, 4-aminocyclopentane methanol, 1-amino ring Hexane methanol, 4-aminocyclohexane methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol and 4 - diethylaminocyclohexane methanol; and an aminocarboxylic acid such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutylene Acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid and 4- Aminocyclohexanecarboxylic acid.

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

Examples of the phenyl group-containing amine include aromatic amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4- Isopropylaniline, 4-n-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline and 4-methyl-N,N-dimethylaniline; aminobenzyl alcohol such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethyl Aminobenzyl alcohol and 4-diethylaminobenzyl alcohol; and aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol and 4-Diethylaminophenol.

Among these organic amine-based compounds, mono(cyclo)alkanolamines and the viewpoints of solubility in a solvent described below and prevention of contamination or film residue on a substrate or a light-shielding layer of an unexposed portion Amino (cyclo)alkanediol is preferred, and 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol 2-Amino-1,3-propanediol and 4-amino-1,2-butanediol are particularly preferred aliphatic amines. Aminophenol is preferred, and 2-aminophenol, 3-aminophenol and 4-aminophenol are particularly preferred phenylamine-containing.

The curing agent is a component which reacts with a carboxyl group and/or a propylene oxide ring contained in the alkali-soluble resin (B) to cure the alkali-soluble resin.

The curing agent is, for example, an epoxy compound or a propylene oxide compound.

The foregoing epoxy compound is preferably a polyfunctional epoxy compound, and examples are aromatic epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F Epoxy resin and novolak epoxy resin; alicyclic epoxy resin, heterocyclic epoxy resin and other epoxy resins, such as glycidyl ester-based resin, glycidylamine as substrate Resin and epoxidized oil; and brominated derivatives of such epoxy resins, epoxidized products of butadiene (co)polymers, and isoprene (co)polymers An epoxidation product, a (co)polymer of a glycidyl group-containing unsaturated compound, and a triglycidyl isocyanurate.

The epoxy group-containing unsaturated compound is also preferably the aforementioned epoxy compound, and examples thereof include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (meth)acrylic acid 6. 7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.

The propylene oxide compound is preferably a polyfunctional propylene oxide compound, and examples thereof are low molecular weight compounds such as dipropylene oxide carbonate, dipropylene oxide adipate, dipropylene oxide terephthalate, Para-propylene dicarboxylate dipropylene oxide and propylene oxide 1,4-cyclohexanedicarboxylate, and high molecular weight compounds, such as propylene oxide etherification products of phenol novolac resin and epoxy (co)polymer of an unsaturated compound of a propane ring structure (excluding copolymer (BI)). The copolymer (BI) has a propylene oxide ring structure and falls under the range of propylene oxide compounds as a curing agent.

A compound having both a propylene oxide ring structure and an unsaturated double bond is also a preferred propylene oxide compound, and examples thereof include the aforementioned propylene oxide unsaturated compound.

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

The amount of the curing agent is preferably 30% by weight or less, more preferably 20% by weight or less based on the total solid content of the radiation-sensitive composition. When the amount of the curing agent is more than 30% by weight, the storage stability of the resulting radiation-sensitive composition may be lowered.

The curing assistant is a component which enhances the curing reaction of the curing agent by subjecting the epoxy group and/or the propylene oxide ring of the curing agent to ring-opening reaction.

The curing assistant is, for example, a polycarboxylic acid, a polycarboxylic acid anhydride, an amine compound or a thermal acid generator.

Examples of the aforementioned polycarboxylic acid include the aforementioned compounds having two or more carboxyl groups in the aforementioned organic acid. Examples of the amine-based compound include the aforementioned organic amine-based compound.

Examples of the above polycarboxylic acid anhydride include aromatic polycarboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride; a polycarboxylic acid anhydride such as isaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, propylene tricarboxylic anhydride, maleic anhydride, and 1,2,3,4-butane tetracarboxylic dianhydride; Alicyclic polycarboxylic anhydrides such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentane tricarboxylic anhydride, 1,2,4-cyclohexane Tricarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride; carboxylic acid anhydride containing ester groups, such as ethylene glycol dibenzotricarboxylic acid anhydride and glycerol triphenylene Triester anhydride; and commercially available under the trade names Adeca Hardener EH-700 (Asahi Denka Kogyo KK), Rikacid HH (Shin Nippon Rika Co., Ltd.) and MH-700 (Shin Nippon Rika Co., Ltd.) Epoxy resin curing agent.

Examples of the aforementioned thermal acid generator include sulfonium salts (excluding the triarylsulfonium salts listed in the aforementioned photopolymerization initiator (D)), benzothiazolium salts, ammonium salts, phosphonium salts, sulfonates a compound, a sulfonimide compound, and a diazomethane compound. Among these compounds, a sulfonium salt, a benzothiazolium salt, a sulfonate compound, a sulfonimide compound, and a diazomethane compound are preferred.

The aforementioned sulfonium salt system includes an alkyl sulfonium salt such as 4-ethenyl phenyl dimethyl sulfonium hexafluoroantimonate, 4-ethenyloxy phenyl dimethyl sulfonium hexafluoroarsenate, hexafluoroantimony. Dimethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hydride, dimethyl-4-(benzylideneoxy)phenylsulfonium hexafluoroantimonate, dimethyl hexafluoroarsenate 4-(benzylideneoxy)phenylthioindole and hexafluoroantimonate dimethyl-3-chloro-4-ethenyloxyphenylthioindole; benzyl sulfonium salt, such as benzyl hexafluoroantimonate 4-hydroxyphenylmethyl sulfonium, benzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, 4-ethenyloxyphenylbenzylmethyl sulfonium hexafluoroantimonate, hexafluoroantimony Benzyl-4-methoxyphenylmethylthioindole, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4 hexafluoroarsenate -hydroxyphenylmethylsulfonium and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate; dibenzylsulfonium salt, such as dibenzyl-4-hydroxybenzene hexafluoroantimonate Thiopurine, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-ethenyloxyphenyldibenzyl hexafluoroantimonate Bismuth, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-hexafluoroantimonate Methyl-4-hydroxy-5-t-butylphenylsulfonium and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate; and substituted benzylsulfonium salt, Such as p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl hexafluorophosphate 4-hydroxyphenylmethylsulfonium, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl hexafluoroantimonate- 4-Hydroxyphenylmethylsulfonium and o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

The aforementioned benzothiazolium salt system includes a benzyl benzothiazolium salt, such as 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, and 3-benzylbenzene tetrafluoroborate. Thiazolidine, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate and 3-benzyl hexafluoroantimonate 5--5-chlorobenzothiazolium.

The aforementioned sulfonate compound includes benzoin tosylate, α-methylolbenzoin tosylate, α-hydroxymethylbenzoin n-octane sulfonate, and pyrogallol tri(trifluoromethanesulfonate). Pyrogallol tris(nonafluoro-n-butane sulfonate), pyrogallol tris(methanesulfonate) and nitrobenzyl-9,10-diethoxyindole-2-sulfonate.

The aforementioned sulfonium imine compound includes N-(trifluoromethanesulfonyloxy) succinimide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine, N-(10-camphorsulfonyloxy) succinimide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene- 2,3 Dimethylimine and N[(5-methyl-5-carboxymethanebicyclo[2.2.1]hept-2-yl)sulfonyloxy]succinimide.

The above diazomethane compounds include bis(cyclohexanesulfonyl)diazomethane, bis(t-butylsulfonyl)diazomethane and bis(1,4-dioxaspiro[4.5] - decane-7-sulfonyl) diazomethane.

Among these thermal acid generators, 4-ethoxycarbonyl phenyl dimethyl sulfonium hexafluoroarsenate, benzyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, 4-ethyl hexafluoroantimonate醯oxyphenylbenzylmethyl sulfonium, dibenzyl-4-hydroxyphenyl sulfonium hexafluoroantimonate, 4-ethenyloxyphenylbenzyl sulfonium hexafluoroantimonate, hexafluoroantimonic acid 3 -Benzylbenzothiazolium and N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine are particularly preferred.

The aforementioned curing assistants may be used singly or in combination of two or more.

The amount of the curing assistant is preferably 15% by weight or less, more preferably 10% by weight or less based on the total solid content of the radiation-sensitive composition. When the amount of the curing assistant is more than 15% by weight, the storage stability of the resulting radiation-sensitive composition may be lowered or the formed coloring layer may be detached from the substrate during development.

Additives other than the aforementioned additives include dispersing aids such as blue pigment derivatives or yellow pigment derivatives such as berberine derivatives; fillers such as glass or alumina; polymer compounds such as polyvinyl alcohol, Polyethylene glycol monoalkyl ether or poly(fluoroalkyl acrylate); nonionic, cationic or anionic surfactant; adhesion accelerator, such as vinyl trimethoxy decane, vinyl triethoxy decane , vinyl tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropyl. methyl. Dimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropyl. methyl. Dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl. methyl. Dimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-hydrothiopropyltrimethoxynonane; antioxidants such as 2,2 '-Thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; UV absorbers such as 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; adhesion inhibitors such as sodium polyacrylate; and thermal radical generators such as 1,1'-azo Bis(cyclohexane-1-carbonitrile) or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent

The radiation-sensitive composition for forming a colored layer of the present invention comprises the above components (A) to (D) as a basic component and optionally the aforementioned additives, and is usually mixed with a solvent to prepare a liquid composition.

A suitable solvent may be selected and used as long as it disperses or dissolves the components (A) to (D) and additives constituting the radiation-sensitive composition, does not react with such components, and has appropriate volatility.

Examples of the solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl Ether, bisethylene glycol monomethyl ether, bisethylene glycol monoethyl ether, bisethylene glycol mono-n-propyl ether, bisethylene glycol mono-n-butyl ether, ginseng ethylene monomethyl Ether, propylene 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 single B Ethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetate, such as Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, bisethylene glycol monomethyl ether acetate, bisethylene glycol monoethyl ether acetate, propylene glycol monomethyl Ether acetate and propylene glycol monoethyl ether acetate; other ethers such as bisglycol dimethyl ether, bisethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketone, Such as Methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactate such as methyl lactate and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycol Ester, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate , n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid Isopropyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate and ethyl 2-oxybutyrate; Aromatic hydrocarbons such as toluene and xylene; and decylamine and decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidinone.

From the viewpoints of solubility, pigment dispersibility, and coatability, among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are used. Ethyl ether acetate, bisethylene glycol dimethyl ether, bisethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropane Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, N-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate are particularly preferred.

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

In addition, high boiling solvents such as benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl b Acid ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate or ethylene glycol monophenyl ether acetate It can be used in combination with the aforementioned solvent.

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

The amount of the solvent is not particularly limited, but from the viewpoint of the coatability and stability of the resulting radiation-sensitive composition, it is desirable to ensure that the total amount of all components except the solvent is preferably 5 in the composition. Up to 50% by weight, particularly preferably from 10 to 40% by weight.

Filter

The filter of the present invention has a coloring layer formed by the radiation sensitive composition of the present invention for forming a colored layer.

A method of forming the coloring layer in the filter of the present invention will be described below.

Forming a light-shielding layer on the surface of the substrate as appropriate to define a portion for forming a pixel, applying a liquid radiation-sensitive composition (including, for example, a red pigment dispersed therein) to the substrate, pre-baking to evaporate the solvent And a coating film is formed.

The coating film is then exposed to radiation via a reticle, developed with an alkali developer, dissolved and removed from the unexposed portions of the coating film, and post-baked to form a pixel array having a predetermined red pixel pattern.

Thereafter, applying, pre-baking, exposing, developing, and post-baking the liquid radiation-sensitive composition containing the green and blue pigment dispersed therein to form a green pixel array sequentially on the same substrate and A blue pixel array is used to obtain a filter having a red, green, and blue pixel array on the substrate. The order in which the color pixels are formed by the present invention is not limited to the foregoing.

The black matrix can likewise be formed using a liquid radiation-sensitive composition comprising, for example, a black pigment dispersed therein.

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

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

When the liquid radiation-sensitive composition is applied to the substrate, a suitable coating technique such as spraying, roll coating, spin coating (spin coating), slit extrusion coating, rod coating or Inkjet coating method. Among these methods, a spin coating method and a slit extrusion coating method are preferred.

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

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

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

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

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

Spray-type development, spray development, dipping (soaking) development, or puddle development can be employed. As the developing conditions, the coating film is preferably developed at room temperature for 5 to 300 seconds.

The obtained filter of the present invention is extremely useful for a transmissive and reflective type color liquid crystal display device, a color imaging device, a color sensor, and the like.

Color liquid crystal display device

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

As an example of the color liquid crystal display device of the present invention, the radiation sensitive composition for forming a coloring layer of the present invention can be used to form a pixel and/or a black matrix on an array of a thin film transistor substrate as described above, and has excellent characteristics. A color liquid crystal display device.

The radiation-sensitive composition for forming a coloring layer of the present invention comprises the aforementioned components (A) to (D) as a basic component. A particularly good example of the composition is described below.

(1) a radiation-sensitive composition for forming a coloring layer, wherein the alkali-soluble resin (B) comprises a copolymer (BII) (2) for forming a radiation-sensitive composition (2) of a coloring layer, wherein The copolymer (II) is at least one selected from the group consisting of copolymers (BI-1) to (BI-6) (3) for forming a color-sensitive layer of the radiation-sensitive composition (1) or (2), wherein the polyfunctional The monomer (C) is a radiation-sensitive composition selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol hexaacrylate (4) for forming a colored layer. (1), (2) or (3), wherein the photopolymerization initiator (D) is at least one compound selected from the group consisting of acetonitrile-based compounds, biimidazole-based compounds, and The compound (5) is a radiation-sensitive composition (1), (2), (3) or (4) for forming a coloring layer, wherein the coloring agent (A) is an organic pigment or carbon black.

Preferably, the filter (6) of the present invention has pixels formed by the radiation-sensitive composition (1), (2), (3), (4) or (5) used to form the colored layer and/or Black matrix.

Preferably, the color liquid crystal display device (7) of the present invention comprises the foregoing filter (6), and more preferably, the color liquid crystal display device (8) of the present invention comprises the aforementioned filter (6) on the thin film transistor substrate array. ).

As described above, the radiation-sensitive composition for forming a colored layer of the present invention has storage stability of the alkali-soluble resin itself, storage stability of the pigment dispersion, and storage stability of the liquid composition even when the pigment content is high. It is extremely excellent, and even if the exposure amount is low, there is no problem that the film retention is lowered, the edge portion of the pattern is missing, and the side etching is caused, and the pixel and the black matrix having excellent solvent resistance and adhesion to the substrate are provided.

Accordingly, the radiation-sensitive composition of the present invention for forming a colored layer is highly advantageous for the manufacture of filters for the electronics industry, such as filters for use in color liquid crystal display devices.

Example

The following examples are intended to further illustrate the invention, but are in no way intended to be limiting.

Synthesis of alkali soluble resin Synthesis Example 1

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 60 parts by weight of benzyl methacrylate, 15 parts by weight of 3-(methacryloxymethyl)-3-ethyl propylene oxide, 10 parts by weight of tricyclomethyth[5.2.1.0 ²⁶ ]癸-8 The ester and 3 parts by weight of α-methylstyrene dimer (as a molecular weight controlling agent) were fed into the flask, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a copolymer (BII) solution. This copolymer (BII) is referred to as an alkali-soluble resin (B-1).

Synthesis Example 2

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 20 parts by weight of benzyl methacrylate, 30 parts by weight of 3-(methacryloxymethyl)-3-ethyl propylene oxide, 10 parts by weight of styrene, and 25 parts by weight of tricyclomethacrylate [5.2. 1.0 ^2.6 ] 癸-8-ester and 3 parts by weight of α-methylstyrene dimer (as a molecular weight controlling agent) were fed into the flask, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a copolymer (BII) solution. This copolymer (BII) is referred to as an alkali-soluble resin (B-2).

Synthesis Example 3

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 20 parts by weight of N-phenyl maleimide, 30 parts by weight of 3-(methacryloxymethyl)-3-ethyl propylene oxide, 10 parts by weight of styrene, 25 parts by weight of methyl Tricyclo[5.2.1.0 ^2.6 ]癸-8-ester and 3 parts by weight of α-methylstyrene dimer (as a molecular weight controlling agent) were fed into the flask, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a copolymer (BII) solution. This copolymer (BII) is referred to as an alkali-soluble resin (B-3).

Synthesis Example 4

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 20 parts by weight of N-phenyl maleimide, 30 parts by weight of 3-(methacryloxymethyl) propylene oxide, 10 parts by weight of styrene, and 25 parts by weight of tricyclomethacrylate [5.2] .1.0 ^2.6 ]癸-8-ester and 3 parts by weight of α-methylstyrene dimer (as a molecular weight controlling agent) were fed into the flask, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a copolymer (BII) solution. This copolymer (BII) is referred to as an alkali-soluble resin (B-4).

Comparative Synthesis Example 1

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 70 parts by weight of benzyl methacrylate, 15 parts by weight of 3-(methacryloxymethyl)-3-ethyl propylene oxide and 3 parts by weight of α-methylstyrene dimer (as molecular weight control agent) It was fed into the flask, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a solution of an alkali-soluble resin. This alkali-soluble resin is called an alkali-soluble resin (B-5).

Comparative Synthesis Example 2

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 25 parts by weight of benzyl methacrylate, 30 parts by weight of 3-(methacryloxymethyl)-3-ethyl propylene oxide, 10 parts by weight of styrene, 20 parts by weight of N-phenylhhenylene Iridinium and 3 parts by weight of α-methylstyrene dimer (as a molecular weight controlling agent) were fed into the flask, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a solution of an alkali-soluble resin. This alkali-soluble resin is called an alkali-soluble resin (B-6).

Comparative Synthesis Example 3

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid, 70 parts by weight of benzyl methacrylate, 15 parts by weight of 3-(methacryloxymethyl) propylene oxide, and 3 parts by weight of α-methylstyrene dimer (as a molecular weight controlling agent) were fed into the flask. Inside, and the inside of the flask was replaced with nitrogen. The resulting mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and polymerized by maintaining the temperature for 5 hours to obtain a solution of an alkali-soluble resin. This alkali-soluble resin is called an alkali-soluble resin (B-7).

Evaluation of storage stability of alkali-soluble resins

The ELD viscosity of Tokyo Keiki Co., Ltd. was used after placing the solution of the alkali-soluble resin prepared in the above Synthesis Example and Comparative Synthesis Example in a glass bottle and holding it in a wet bath at 40 ° C isothermal for 3 weeks. The viscosity of the solution before and after storage was measured (25 ° C) to evaluate the viscosity change rate (viscosity after storage x 100 / viscosity before storage). The evaluation results are shown in Table 1.

Preparation of pigment dispersion Preparation Example 1

20 parts by weight of a mixture of CI Pigment Red 254/CI Pigment Red 177 as a colorant (A) in a weight ratio of 80/20, 5 parts by weight (solid content) as a dispersing agent, BYK-2001 and 75 parts by weight as a solvent Propylene glycol monomethyl ether acetate was mixed by a bead mill to prepare a pigment dispersion (R1).

Preparation Example 2

The pigment dispersion (R2) was prepared in the same manner as in Preparation Example 1, except that 5 parts by weight (solid content) of Solsperse 24000 was used in place of BYK-2001 as a dispersing agent.

Preparation Example 3

20 parts by weight of a mixture of CI Pigment Green 36/C.1. Pigment Yellow 150 as a coloring agent (A) in a weight ratio of 50/50, 5 parts by weight (solid content) as a dispersing agent, BYK-2001 and 75 parts by weight Propylene glycol monomethyl ether acetate as a solvent was mixed by a bead mill to prepare a pigment dispersion (G1).

Preparation Example 4

A pigment dispersion (G2) was prepared according to the method of Preparation Example 3, except that 5 parts by weight (solid content) of Solsperse 24000 was used in place of BYK-2001 as a dispersing agent.

Preparation Example 5

20 parts by weight of BYK-2001 and 75 parts by weight of CI Pigment Blue 15:6/CI Pigment Violet 23 as a coloring agent (A) in a weight ratio of 90/10, 5 parts by weight (solid content) as a dispersing agent The solvent propylene glycol monomethyl ether acetate was mixed by a bead mill to prepare a pigment dispersion (B1).

Preparation Example 6

A pigment dispersion (B2) was prepared according to the method of Preparation Example 5, except that 5 parts by weight (solid content) of Solsperse 24000 was used in place of BYK-2001 as a dispersing agent.

Example 1

100 parts by weight of the pigment dispersion (R1) as the colorant (A), 15 parts by weight (solid content) as the alkali-soluble resin (B-1) of the alkali-soluble resin (B), and 15 parts by weight as a polyfunctional single Diisopentaerythritol hexaacrylate (C), 5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine as photopolymerization initiator (D) The propane-1-one is used in an amount such that propylene glycol monomethyl ether acetate as a solvent is mixed at a solid content of 25% to prepare a liquid composition (R1-1).

The liquid composition (R1-1) was patterned by the following method for evaluation. The evaluation results are shown in Table 8.

Pattern formation

The liquid composition (R1-1) was applied to the surface of the glass substrate by a spin coater, and prebaked at 90 ° C for 4 minutes to form a 1.3 μm thick coating film. Thereafter, 6 of the substrates were cooled to room temperature, and the coating film on the substrate was individually exposed to 300 J/m ² , 400 J/m ² , 500 J/m ² , 750 J/ via a mask using a high pressure mercury lamp. Radiation of m ² , 1,000 J/m ² and 2,000 J/m ² . The coating film was spray-developed at a temperature of 23 ° C under a developing pressure of 1 kgf/cm ² with a 0.04% by weight aqueous potassium hydroxide solution (nozzle diameter of 1 mm), and baked at 220 ° C for 30 minutes to form a 200 x 200 micron dot. Shaped pattern.

Sensitivity assessment

The dot pattern formed on the substrate with the aforementioned exposure amount was evaluated by observation. ○ indicates that the formation of the pattern is intact, and the film retention (film thickness after development × 100 / film thickness before development) calculated by the film thickness ratio before and after development is 90% or more, and Δ indicates that the pattern is formed intact, but The film retention ratio calculated based on the film thickness ratio before and after development was less than 90% or a partial deletion of the pattern was found, and the × line indicates that the circle was not formed.

Evaluation of solvent resistance

The six-piece substrate irradiated with the aforementioned exposure amount was immersed in N-methylpyrrolidone at 25 ° C for 30 minutes, and then the dot pattern before and after the immersion was observed by a scanning electron microscope to evaluate. ○ indicates that the formation pattern remains unchanged and the film thickness ratio before and after the immersion (film thickness after immersion x 100 / film thickness before immersion) is 95% or higher, and Δ indicates that the film thickness ratio before and after immersion is less than 95% or Part of the pattern is missing, and x indicates that all patterns are peeled off from the substrate after immersion. When the substrate cannot be formed intact due to insufficient sensitivity, it is not evaluated (indicated by "-" in Tables 8 to 11).

Adhesion assessment

The liquid composition (R1-1) was applied to the surface of the glass substrate by a spin coater, and baked at 90 ° C for 4 minutes to form a 1.3 μm thick coating film. Thereafter, the substrate was cooled to room temperature, and the coating film was exposed to 2,000 J/m ^{2 of the} radiation with a high pressure mercury lamp. The coating film was then spray-developed at a temperature of 23 ° C under a developing pressure of 1 kgf/cm ² with a 0.04% by weight aqueous potassium hydroxide solution (nozzle diameter: 1 mm), and baked at 220 ° C for 30 minutes. Thereafter, the coating film was cut into 100 squares in accordance with JIS K5400 to carry out an adhesion test. ○ indicates no square peeling, △ indicates that there are 1 to 10 squares peeling off, and × indicates that there are more than 10 squares peeling off.

Evaluation of storage stability of liquid compositions

When the liquid composition (R1-1) was placed in a glass bottle and kept in a thermo-hygrostat at 40 ° C for one week, the viscosity of the liquid composition before and after storage was measured to calculate the viscosity change rate (viscosity after storage). ×100/viscosity before storage).

Examples 2 to 40 and Comparative Examples 1 to 30

The liquid composition was prepared and evaluated in the same manner as in Example 1. The type and amount of the components of the liquid composition at different points were changed as shown in Tables 2 to 7 (parts by weight). The evaluation results are shown in Tables 8 to 11.

The series of polyfunctional monomers, photopolymerization initiators, additives and solvents in Tables 2 to 7 are shown below.

Polyfunctional monomer C-1: diisopentyltetraol hexaacrylate

Photopolymerization initiator D-1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one D-2: 1-[9-ethyl- 6-(2-methylbenzylidene)-9.H.-oxazol-3-yl]ethanone-1-(O-acetamidine) D-3: 2,4-diethylthioxanthone

Additive E-1: bisphenol A novolac epoxy resin (trademark: 157S65 of Japan Epoxy Resin Co., Ltd.) E-2: trimellitic anhydride E-3: N-(trifluoromethanesulfonyloxy) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine

Claims (5)

A radiation-sensitive composition for forming a colored layer comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein the alkali is soluble The resin (B) is one containing (b1) at least one member selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic anhydrides and unsaturated phenol compounds, (b2) an unsaturated compound having an alicyclic carbocyclic structure, and (b3) having a ring. A copolymer of an oxypropane ring structure unsaturated compound and (b4) an unsaturated quinoid. The radiation-sensitive composition for forming a coloring layer according to the first aspect of the patent application, wherein the alkali-soluble resin (B) is a copolymer comprising the following monomers as a basic monomer: (b1) includes (a) An unsaturated acid compound having an acrylic acid as an essential component, (b2) an unsaturated alicyclic compound selected from the group consisting of cyclohexyl (meth)acrylate and (meth)acrylic acid Unsaturated epoxy compound oxide of the group consisting of esters and (meth) acrylate, tricyclo [5.2.1.0 ^2.6] decan-8-acetate, (b3) selected from the following: 3 - [(meth) Bing Xixi oxygen Methyl] propylene oxide, 3-[(meth)acryloxymethyl]-3-ethyl propylene oxide, 3-[(methyl) propylene methoxymethyl]-2-trifluoro Methyl propylene oxide, 3-[(meth)acryloxymethyl]-2-phenyl propylene oxide, 2-[(meth) propylene methoxymethyl] propylene oxide and 2-[ (Meth) propylene methoxymethyl]-4-trifluoromethyl propylene oxide, and (b4) N-phenyl maleimide. The radiation-sensitive composition for forming a coloring layer according to the first aspect of the patent application, wherein the (D) photopolymerization initiator contains a compound having O-mercaptopurine as a substrate. A color filter having a coloring layer formed of a radiation-sensitive composition for forming a coloring layer according to any one of claims 1 to 3. A color liquid crystal display device comprising the filter of claim 4 of the patent application.