TWI493281B - Radiation-sensitive composition for forming coloring layer, color filter and color liquid crystay display element - Google Patents

Description

Radiation-sensitive composition for coloring layer formation, color filter, and color liquid crystal display element

The present invention relates to a radiation sensitive composition for forming a coloring layer, a color filter, and a color liquid crystal display element. More specifically, it relates to a color liquid crystal display device capable of transmitting or reflecting type, and color imaging. A color filter used for a tube element or the like forms a radiation-sensitive composition for use in a useful coloring layer, a color filter having a coloring layer formed of the radiation-sensitive composition, and a color filter having the color filter Color liquid crystal display element.

A method of forming a color filter using a color-sensing radiation-linear composition, and a coating film having a color-sensitive radioactive composition formed on a substrate or a substrate on which a light-shielding layer requiring a pattern is formed in advance is known, and has a The mask of the predetermined pattern is irradiated with radiation (hereinafter referred to as "exposure"), and the unexposed portion is developed and dissolved, and then post-baking is performed to obtain pixels of respective colors (for example, refer to Patent Documents 1 and 2).

Further, in recent years, in the technical field of color filters, the reduction of the exposure amount and the shortening of the production time have become mainstream, and in order to cope with the high color purity required for the color liquid crystal display element, the pigment occupies in the coloring sensitizing radioactive composition. The content ratio tends to increase gradually. As described above, when the content ratio of the pigment occupied by the coloring radiation-reactive composition is increased, and the amount of exposure when the pixel pattern is formed is lowered, the cross-sectional shape of the pixel pattern tends to become a reverse cone (overhang). As a result, the problem of disconnection of the transparent electrode such as ITO formed on the pixel pattern is conspicuous.

The cross-sectional shape of the pattern shape is a problem of a reverse cone. For example, Patent Documents 3 and 4 disclose the use of a composition containing a chain transfer agent. However, in such a method, when the exposure amount is lowered, it is difficult to form a pixel pattern having a sufficient residual film ratio or adhesion. Further, even if the cross-sectional shape is a straight cone, if the taper angle is too gentle, the inclined portion of the pixel pattern becomes long, and a portion where the film thickness is thinned at the edge of the pixel causes a failure in reproducing a desired color.

Moreover, in the mass production process of color filters, the problem of unevenness in inspection process and low production efficiency caused by various foreign matter or color unevenness in various processes is also apparent.

[Previous Technical Literature]

[Patent Document 1] JP-A-2-144502

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

[Patent Document 3] Japanese Patent Publication No. 2002-167404

[Patent Document 4] Japanese Patent Publication No. 2002-287337

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel coloring layer-forming radiation sensitive composition for a pixel which can form an appropriate tapered shape and has excellent residual film ratio or adhesion even at a low exposure amount. .

Further, an object of the present invention is to provide a color filter including a pixel formed of the photosensitive layer forming radiation sensitive composition, and a color liquid crystal display element including the color filter.

In view of such a situation, the present inventors have found that a specific amount of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in a molecule is used as a coloring layer forming feeling of a polyfunctional monomer. The radiation linear composition can solve the above problems, and the present invention has been completed.

That is, the present invention is a radiation sensitive composition for forming a coloring layer, which comprises (A) a coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The radiation-sensitive composition for forming a color layer containing 100 to 300 parts by weight of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule with respect to 100 parts by weight of the (B) alkali-soluble resin. As (C) a polyfunctional monomer.

Moreover, the present invention provides a color liquid crystal display element including the pixel formed using the radiation sensitive composition and the color filter.

According to the radiation sensitive linear composition of the present invention, the amount of exposure can be reduced and the production time can be shortened, and even if the content ratio of the pigment which is contained in the coloring sensitizing radioactive composition becomes high, an appropriate tapered shape can be formed and the residue can be formed. A pixel pattern excellent in film rate or adhesion. Further, according to the radiation sensitive composition of the present invention, the color filter can be manufactured with high production efficiency.

Therefore, the radiation sensitive composition of the present invention is very suitable for use in the production of color filters for various applications such as color filters for color liquid crystal display elements, color image sensor elements, and color sensors, which are the first in the electronics industry.

[Best Mode for Carrying Out the Invention]

Sensitive radioactive composition for coloring layer formation

The "colored layer" of the sensitizing radiation-forming composition for forming a coloring layer of the present invention (hereinafter, referred to simply as "a radiation-sensitive composition") means a pixel and/or black used for a color filter. The layer formed by the matrix.

Hereinafter, the constituent components of the radiation sensitive composition for forming a colored layer of the present invention will be described.

- (A) colorant -

The coloring agent (A) of the present invention is not particularly limited, and may be any of an organic pigment and an inorganic pigment.

The organic pigment may, for example, be a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), and specifically, the following color may be mentioned. Index (CI) number. However, the present invention is not limited to this.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, 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 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2. CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, 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 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38; CI Pigment Blue 1 5, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, CI Pigment Blue 80; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7.

In the present invention, the organic pigment can also be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Further, examples of the inorganic pigment include titanium oxide, barium sulfate, and carbonic acid. Calcium, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine blue, indigo, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, and Carbon black and so on.

These coloring agents can also be used by modifying the surface of the particles using a polymer as needed. For example, a polymer described in Japanese Laid-Open Patent Publication No. Hei 8-259876, or a commercially available polymer or oligomer for pigment dispersion can be used. The method of coating the polymer on the surface of the carbon black is disclosed in, for example, JP-A-H09-71733, JP-A-9-95625, and JP-A-9-124969.

These coloring agents can be used alone or in combination of two or more.

When the radiation sensitive composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development and heat resistance, the colorant (A) is a coloring agent having high color developability and high heat resistance, particularly A coloring agent having high heat decomposition resistance is preferred, and an organic coloring agent is particularly preferred, and an organic pigment is particularly preferred.

On the other hand, when the radiation sensitive composition of the present invention is used to form a black matrix, since the black matrix is required to have light shielding properties, the coloring agent (A) is preferably an organic pigment or carbon black.

When the content of the coloring agent of the radiation sensitive composition of the present invention is 30% by weight or more based on the total solid content of the radiation sensitive composition, it can be formed into an appropriate smooth shape and excellent in residual film ratio or adhesion. Pixels. Further, in the present invention, the content of the colorant is preferably 70% by weight or less, and particularly preferably 60% by weight or less, based on the total solid content of the radiation sensitive composition from the viewpoint of ensuring development. Here, the solid component is a solvent described later Other ingredients.

The coloring agent of the present invention can be used together with a dispersing agent and a dispersing aid as needed.

As the dispersing agent, for example, a suitable dispersing agent such as a cationic type, an anionic type, a nonionic type or an amphoteric type can be used, and a polymer dispersing agent is preferred. Specific examples thereof include alkyl ammonium salts or phosphate salts of modified acrylic copolymers, acrylic copolymers, polyurethanes, polyesters, and polymer copolymers, and cationic comb-type graft polymers. Wait. Here, the cationic comb-type graft polymer means a molecule of a dry polymer having a plurality of basic groups (cationic functional groups) and grafting a branched polymer of 2 or more molecules. The polymer of the structure, for example, the dry polymer portion may be a polyamidene, and the branched polymer may be a polymer composed of a ring-opening polymer of ε -caprolactone. Among these dispersants, a modified acrylic copolymer, a polyurethane, and a cationic comb-type graft polymer are preferred.

Such a dispersing agent can be obtained commercially, and examples of the modified acrylic copolymer include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, BYK-Chemie (BYK)), and polyamine. Examples of the carbamate include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK-Chemie (BYK)), SOLSPERSE 76500 (LUBRIZOL) The cationic comb-type graft polymer may, for example, be SOLSPERSE 24000 (manufactured by LUBRIZOL Co., Ltd.), AJISPER PB821 or AJISPER PB822 (manufactured by Ajinomoto-Fine-Techno Co., Ltd.).

These dispersing agents may be used alone or in combination of two or more. The content of the dispersant is preferably 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, per 100 parts by weight of the (A) coloring agent. Good, especially 10 to 50 parts by weight.

The dispersing aid may, for example, be a blue pigment derivative or a yellow pigment derivative, and specific examples thereof include a copper phthalocyanine derivative.

- (B) alkali soluble resin -

The (B) alkali-soluble resin of the radiation-sensitive composition of the present invention is not particularly limited as long as it is soluble in the alkaline developing solution used in the development process for forming the colored layer, and usually has a carboxyl group. A polymer of an acidic functional group such as a phenolic hydroxyl group. Among them, those having a polymer having a carboxyl group are preferred, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "carboxyl group-containing unsaturated monomer" and other copolymerizable ethylenically unsaturated monomers. A copolymer of a monomer (hereinafter referred to as "copolymerizable unsaturated monomer") (hereinafter referred to as a "carboxyl group-containing copolymer") is particularly preferable. Further, in the present specification, (meth)acrylic acid is represented. Methacrylic acid or acrylic acid.

The carboxyl group-containing unsaturated monomer may, for example, be an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, α -chloroacrylic acid or cinnamic acid; maleic acid, maleic anhydride, or reversed butene Diacid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid unsaturated dicarboxylic acid or anhydride thereof; such as succinic acid-[2-(methyl)acryloxyethyl a [(meth)acryloxyalkyl] ester of a dibasic or higher polycarboxylic acid of an ester, a [2-(methyl)propenyloxyethyl] phthalate; such as an ω-carboxyl group A (meth) acrylate of a caprolactone-mono (meth) acrylate having a carboxyl group and a hydroxyl group at both terminals.

In the present invention, the carboxyl group-containing unsaturated monomer is (meth)acrylic acid, succinic acid-[2-(methyl)acryloxyethyl)ester, ω-carboxypolycaprolactone-(meth)acrylic acid. Ester and the like are preferred, and (meth)acrylic acid is particularly preferred.

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

Further, examples of the copolymerizable unsaturated monomer include N-phenyl maleimide, N-o-hydroxyphenyl maleimide, and N-m-hydroxyphenylbutylene. Imine, N-p-hydroxyphenyl maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimide-3 - maleimide benzoate, N-succinimide-4 maleimide butyrate, N-succinimide-6-methyleneimine N-position-substituted maleic acid of hexanoate, N-succinimide-3-oxenimide propionate, N-(acridinyl) maleimide Amine; such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy Styrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl Ether, o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, An aromatic vinyl compound of p-vinylbenzylepoxypropyl ether; such as hydrazine, 1-methyl hydrazine; such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate N-propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, (methyl) Cyclohexyl acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxy diglycol (meth) acrylate Ester, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, isodecyl (meth) acrylate, tricyclic [5.2.1.0 ^2,6] dec-8-yl (meth) acrylate Ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide of p-cumylphenol An unsaturated carboxylic acid ester of a modified (meth) acrylate; an unsaturated carboxylic acid glycidyl acrylate such as glycidyl (meth) acrylate; such as vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl carboxylate of vinyl benzoate; other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether; such as (meth)acrylonitrile, alpha -chloropropene a cyanide vinyl compound of a nitrile or a vinylidene cyanide; an unsaturated decylamine such as (meth) acrylamide, α -chloropropenylamine or N-2-hydroxyethyl(meth)acrylamide; An aliphatic conjugated diene such as 1,3-butadiene, isoprene or chloroprene; such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, A macromonomer having a (meth) acrylonitrile group at the end of a polymer molecular chain of polyoxyalkylene.

These copolymerizable unsaturated monomers may be used alone or in combination of two or more.

In the present invention, the copolymerizable unsaturated single system contains a maleimide group selected from the N-position, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and one at the end of the polymer molecular chain. It is preferred that at least one of the group consisting of (meth)acryloyl group-based macromonomers is selected to contain N-phenyl maleimide, N-cyclohexyl-n-butylene Amine, styrene, α -methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, allyl acrylate, benzyl (meth)acrylate, mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, p-cumyl At least one of the group consisting of oxirane-modified (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer of phenol is more preferably selected from the group consisting of N- Phenyl maleimide, N-cyclohexyl maleimide, styrene, α -methylstyrene, methyl (meth)acrylate, n-butyl (meth)acrylate, ( 2-ethylhexyl methacrylate, benzyl (meth) acrylate, mono(meth) acrylate, and ethylene oxide modified (meth) acrylate of p-cumyl phenol At least one of the groups is particularly good.

In the present invention, for example, an acrylic acid-soluble resin obtained by copolymerizing a copolymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and 2-(meth)acryloyloxy group B By reacting an unsaturated isocyanate compound such as a isocyanate, a polymerizable unsaturated bond can be introduced into a side chain of the acrylic acid-soluble resin.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. When the copolymerization ratio is too small, the solubility of the radiation-sensitive composition obtained in the alkaline developing solution tends to be low. On the other hand, when too much, the solubility of the alkaline developing solution becomes too large. When the image is developed using an alkaline developing solution, there is a tendency that the pixel is easily detached from the substrate or the surface of the pixel is easily roughened.

The weight average molecular weight (hereinafter, also referred to as "Mw") converted into polystyrene measured by a gel permeation chromatograph (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin of the present invention is usually 1,000~. 45,000, preferably 3,000~20,000. When the Mw is too small, the residual film ratio of the obtained film may be lowered, or the pattern shape, heat resistance, and the like may be impaired, and the electrical characteristics may be deteriorated. On the other hand, when the Mw is too large, the resolution is lowered. Or the shape of the pattern is impaired, and the application of the slit nozzle method tends to cause dry foreign matter to be easily generated.

Further, the amount of the alkali-soluble resin of the present invention converted into polystyrene is measured by a gel permeation chromatograph (GPC, elution solvent: tetrahydrofuran). The average molecular weight (hereinafter also referred to as "Mn") is usually 1,000 to 45,000, preferably 3,000 to 20,000.

Further, the ratio (Mw/Mn) of Mw to Mn of the alkali-soluble resin of the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 4.0.

The alkali-soluble resin of the present invention can be produced by a known method, and can also be controlled by a method disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. Its structure or Mw, Mw / Mn.

In the present invention, the alkali-soluble resin may be used alone or in combination of two or more.

In the present invention, the content of the (B) alkali-soluble resin is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. When the content of the alkali-soluble resin is too small, for example, the alkali developability is lowered, or there is a possibility that residue or surface contamination occurs on the substrate of the unexposed portion or on the light shielding layer. In contrast, when there is too much, there is a possibility that it is difficult to achieve the target color density of the film because the relative colorant concentration is lowered.

-(C) Polyfunctional monomer -

The polyfunctional single system of the present invention is composed of a monomer having two or more polymerizable unsaturated bonds, and contains 100 to 300 parts by weight of the (B) alkali-soluble resin in an amount of 100 to 300 parts by weight. A compound having a caprolactone structure and two or more polymerizable unsaturated bonds (hereinafter, referred to as a "polyfunctional monomer having a caprolactone structure"), preferably containing 100 to 250 parts by weight. . When the content of the caprolactone-modified polyfunctional monomer is less than 100 parts by weight, the desired effect may be impaired. On the other hand, when it is more than 300 parts by weight, the adhesion to the substrate may be lowered.

A polyfunctional single system containing a caprolactone structure, for example, by trishydroxymethylethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, neopentylol A polyhydric alcohol such as dipentaerythritol, tripentenol, glycerin, diglycerin or trimethylol melamine, which is obtained by esterification with (meth)acrylic acid and ε -caprolactone. A polyfunctional (meth)acrylate containing an ε -caprolactone structure can be mentioned. Among them, a polyfunctional monomer having an ε -caprolactone structure represented by the following formula (1) is preferred from the viewpoint of forming a suitable smooth-shaped pixel even at a low exposure amount.

(In the formula, all of the six R systems are groups represented by the following formula (2), or one to five of the six R groups are groups represented by the following formula (2), and the remainder is a formula (3) the base shown)

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and "*" represents a dangling bond)

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a dangling bond)

Among the compounds represented by the above formula (1), the base represented by the formula (2) is preferably two or more, more preferably three or more, and particularly preferably six.

Such a polyfunctional single system containing a caprolactone structure, for example, a KAYARAD DPCA series commercially available from Nippon Kayaku Co., Ltd., may be exemplified by DPCA-20 (in the above formulas (1) to (3), m=1. , the number of groups represented by formula (2) = 2, R ¹ is a compound in which all hydrogen atoms are), DPCA-30 (the same formula, m = 1, the number of groups represented by formula (2) = 3, R ¹ is a compound in which all hydrogen atoms are), DPCA-60 (the same formula, m=1, the number of groups represented by formula (2) is 6; R ¹ is a compound in which all hydrogen atoms), DPCA-120 (same In the formula, m = 2, the number of groups represented by the formula (2) = 6, R ¹ is a compound in which all hydrogen atoms are used, and the like.

In the present invention, the polyfunctional monomer having a caprolactone structure may be used alone or in combination of two or more.

In the present invention, in order to increase the residual film ratio, it is preferable to use a polyfunctional monomer having a caprolactone structure in combination with other polyfunctional monomers, and to have two structures without a caprolactone structure. The above compound of a polymerizable unsaturated bond is particularly preferably used.

Examples of the other polyfunctional monomer include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and polyalkylene glycols such as polyethylene glycol and polypropylene glycol. (methyl) propyl a poly (meth) acrylate of a trihydric or higher polyhydric alcohol such as glycerin, trimethylolpropane, neopentyl alcohol or dipentaerythritol or a modified product of the same; Oligo(meth)acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, enamel resin, and spiro resin; two-terminal hydroxyl poly-1,3-butadiene, two Di(meth)acrylates of terminal hydroxylated polymers of terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactones, etc.; gin[2-(methyl)acryloxyethyl]phosphate Or isomeric cyanuric acid ethylene oxide modified triacrylate.

Among these other polyfunctional monomers, a poly(meth)acrylate of a trihydric or higher polyhydric alcohol or a modified product of the dicarboxylic acid, specifically, trimethylolpropane triacrylate Ester, trimethylolpropane trimethacrylate, neopentyl alcohol triacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, two Pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol triacrylate and succinic acid Monoester, monopentate of neopentyl glycol pentaacrylate and succinic acid, monoester of dipentaerythritol pentaacrylate and succinic acid, monopentaerythritol penta methacrylate and succinic acid The esterified product is preferable because the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and surface contamination, residual film, and the like are less likely to occur on the substrate of the unexposed portion and the shielding layer, and trimethylolpropane triacrylate is used. , pentaerythritol triacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, neopentyl glycol triacrylate and monoester of succinic acid, and monoester of dipentaerythritol pentaacrylate and succinic acid good.

The above other polyfunctional single system may be used singly or in combination of two or more.

The content of the (C) polyfunctional monomer in the present invention is preferably 100 to 400 parts by weight, more preferably 100 to 300 parts by weight, per 100 parts by weight of the (B) alkali-soluble resin. When the total content is too small, there is a possibility that the desired effect of the present invention is impaired. On the other hand, if there are too many, for example, the alkali developability is lowered, or the surface contamination is likely to occur on the substrate or the shielding layer of the unexposed portion. And the tendency of residual film.

Further, the content ratio of the polycaptanyl monomer having a caprolactone structure in the (C) polyfunctional monomer is preferably from 25 to 100% by weight, more preferably from 50 to 75% by weight. By using a polyfunctional monomer having a caprolactone structure at such a ratio, an appropriate smooth tapered pixel can be formed even at a low exposure amount.

Further, in the present invention, a part of the polyfunctional monomer can be substituted with a monofunctional monomer having one polymerizable unsaturated bond.

The monofunctional monomer may, for example, be bisuccinic acid mono [2-(methyl) propylene oxiranyl ethyl ester] or citric acid mono [2-(methyl) propylene methoxyethyl ester] One [(meth) propylene decyloxyalkyl] ester of a polyvalent carboxylic acid or more, and one of a polymer having a carboxyl group and a hydroxyl group at both ends of the ω-carboxypolycaprolactone mono(meth) acrylate ( Other than methyl acrylate, N-(methyl) propylene sulfhydryl porphyrin, N-vinyl pyrrolidone, N-vinyl-ε-caprolactam, etc., commercially available products are M-5600 ( Trade name, East Asian synthetic (share) system, etc.

These monofunctional monomers may be used alone or in combination of two or more. The content ratio of the monofunctional monomer is relative to the polyfunctional monomer and the monofunctional single The total amount of the particles is usually 90% by weight or less, preferably 50% by weight or less. When the content ratio of the monofunctional monomer is too large, the strength or surface smoothness of the obtained colored layer may be insufficient.

-(D) Photopolymerization Initiator -

In the photopolymerization initiator of the present invention, the (C) polyfunctional monomer and the monofunctional monomer used as the case may be exposed by radiation such as visible light, ultraviolet light, far ultraviolet ray, electron ray or X-ray. The polymerization begins to produce a compound of the active species.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a diimidazole compound, and the like. Compound, O-antimony compound, sulfonium salt compound, benzoin compound, diphenyl ketone compound, α -diketone compound, polynuclear benzoquinone compound, xanthone compound, diazo system a compound, a quinone imide sulfonate compound, or the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator of the present invention contains a compound selected from the group consisting of a thioxanthone compound, an acetophenone compound, a diimidazole compound, and three. At least one of the group consisting of a compound and an O-lanthanoid compound is preferred.

Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.

Further, specific examples of the acetaminophen compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one and 2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamine Keto)-1-(4-morpholinephenyl)butan-1-one.

Further, specific examples of the diimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2 , 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2,4,6 -Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and the like.

Further, when a diimidazole-based compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor in combination in order to improve the sensitivity. Here, the "hydrogen donor" means a compound capable of imparting a hydrogen atom to a radical generated from a diimidazole compound by exposure. The hydrogen donor may, for example, be 2-hydrothiobenzothiazole or 2-hydrothiobenzophenone. An amine-based hydrogen donor such as a thiol-based hydrogen donor such as oxazole, 4,4′-bis(dimethylamino)diphenyl ketone or 4,4′-bis(diethylamino)diphenyl ketone . In the present invention, the hydrogen donor can be used singly or in combination of two or more kinds, and it is preferable to use one or more kinds of thiol-based hydrogen donors and one or more amine-based hydrogen donors in combination. .

Again, the aforementioned three Specific examples of the compound include 2,4,6-para(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s- ,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 ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halomethyl groups a compound.

Further, specific examples of the O-lanthanoid compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzamide), 1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidine), 1-[9-ethyl- 6-(2-Methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone-1-(O-acetamidine), 1-[9-B -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidenyl}-9H-indazol-3-yl] - Ethyl ketone-1-(O-acetamidine) and the like.

In the present invention, when a photo-radical generator other than a diimidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Such a sensitizer may, for example, be 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, or 4-diethylamino group B. Toluene, 4-dimethylaminopropione, ethyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2-hexyl acetate, 2,5-bis(4-diethylamino) Benzylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is usually 0.01 to 120 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the (C) polyfunctional monomer. When the content of the photopolymerization initiator is too small, there is a possibility that the curing by the exposure becomes insufficient, or it is difficult to obtain a color filter in which the colored layer pattern is formed according to the specification, and on the other hand, the colored layer is formed. There is a tendency to easily fall off from the substrate.

-additive-

The radiation sensitive composition of the present invention contains the above components (A) to (D), but may further contain other additives as necessary.

Here, other additives may be filled with, for example, glass, alumina, or the like. a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a nonionic surfactant, a cationic surfactant, or an anionic surfactant; vinyl trimethoxy Decane, vinyltriethoxydecane, vinyl ginseng (2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-epoxypropoxy Propylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxy Adhesion promoters such as decane, 3-methacryloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, etc.; 2,2-thiobis(4-methyl-6- An antioxidant such as a third butyl phenol) or a 2,6-di-tert-butylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzo Ultraviolet absorber such as triazole or alkoxydiphenyl ketone; anti-agglomerating agent such as sodium polyacrylate; , Adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like alkali solubility improvers.

- solvent -

In the sensitizing radioactive composition for forming a coloring layer of the present invention, the components (A) to (D) are used as essential components, and the additive component is contained as necessary, and usually a solvent is prepared to prepare a liquid composition.

The solvent can be appropriately selected and used as long as it can dissolve or disperse the components (A) to (D) or the additive component and does not react with the components and has appropriate volatility.

Such a solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol mono-n-propyl group. Ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol-a Ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, di-propylene glycol monomethyl ether, dipropylene glycol-B (poly)alkylene glycol monoalkyl ethers such as phenyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri-propylene glycol monomethyl ether, tri-propylene glycol monoethyl ether Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl (poly)alkyl 2, such as ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Alcohol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone Ketones such as 2-heptanone and 3-heptanone Lactic acid alkyl esters such as methyl lactate and ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Methyl oxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methyl Oxybutyl butyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate, 2 - side oxybutyrate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; decylamines such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or the like Indoleamines, etc.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol-B are from the viewpoints of solubility, pigment dispersibility, and coatability. Ethyl acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, lactate B Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, acetic acid Butyl ester, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. are preferred.

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

Further, a benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol or benzyl acetate may be used together with the solvent. A high boiling point solvent such as ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate.

These high-boiling point solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, and the total concentration of each component after the solvent is removed from the composition is usually 5 to 50% by weight from the viewpoints of applicability, stability, and the like of the obtained radiation-sensitive composition. An amount of 40% by weight is preferred.

In the present invention, the radiation sensitive composition can be prepared by an appropriate method, for example, by mixing the components (A) to (D) with a solvent or an additive to separate the pigment in a solvent and dispersing the agent. In the presence of a dispersing aid to be added, if necessary, a part of the component (B) is used together with, for example, a bead mill, a roll mill, etc., and mixed and dispersed while being pulverized to prepare a pigment dispersion liquid, which is added thereto. It is preferred to prepare the components (B) to (D) and, if necessary, additional solvents or additives.

- Method of forming a color filter -

Next, a method of forming the color filter of the present invention using the radiation sensitive composition of the present invention will be described.

The method of forming a color filter usually includes at least the following processes (1) to (4).

(1) A process for forming a coating film of the radiation sensitive composition of the present invention on a substrate.

(2) A process of exposing at least a part of the aforementioned coating film.

(3) A process of developing the exposed coating film.

(4) The process of post-baking after filming.

Hereinafter, the processes will be described in order.

(1) Process

First, a light shielding layer (black matrix) is formed on the surface of the substrate in such a manner as to form a pixel portion, and a radiation sensitive composition of the present invention containing, for example, a red (A) colorant is formed on the substrate. Usually, after coating with a liquid composition, the coating film is formed by prebaking and evaporating the solvent.

The substrate to be used in the process may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidimide, polyimide or polyether, and examples thereof include a ring. A ring-opening polymer of an olefin or a hydrogen additive thereof.

Further, these substrates may be subjected to an appropriate pretreatment such as a drug treatment, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition using a decane coupling agent or the like as needed.

When the liquid composition is applied to the substrate, a suitable coating method such as a spin coating method, a cast coating method, a roll coating method, or a coating method using a slit die coater can be used, and a spin coating method or a slit can be used. The coating method of the die coater is preferably the same.

The prebaking conditions are usually 70 to 110 ° C for about 2 to 4 minutes. Further, according to the radiation sensitive composition of the present invention, even if the prebaking process is omitted, the pixel and the black matrix can be formed.

The coating thickness is usually 1.0 to 10 μm after solvent removal, preferably 1.0 to 6.0 μm, and particularly preferably 1.0 to 4.0 μm.

(2) Process

Subsequently, at least a portion of the formed coating film is exposed. At this time, a part of the exposure of the coating film is usually exposed through a photomask having a predetermined pattern.

For the radiation to be used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray can be used, and radiation having a wavelength of 190 to 450 nm is preferable.

The exposure amount of the radiation is usually 10 to 10,000 J/m ² . According to the radiation sensitive composition of the present invention, even in the case of an exposure amount of 800 J/m ² or less and an exposure amount of 600 J/m ² or less, it is possible to form a pixel having an appropriate smooth shape and excellent residual film ratio and adhesion. Moreover, from the viewpoint of controllability when using a light source having a high illuminance, the lower limit of the exposure amount is preferably 200 J/m ² or more.

(3) Process

Subsequently, the unexposed portion of the coating film is dissolved and removed using a developing solution, preferably an alkaline developing solution.

The alkaline imaging solution is, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1 An aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene or the like is preferred.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developing solution in an appropriate amount.

As the development processing method, a shower imaging method, a spray imaging method, a dip imaging method, a puddle type development method, or the like can be applied.

The development condition is preferably about 10 to 300 seconds at room temperature.

- (4) Process -

Subsequently, by baking the developed coating film, it is possible to obtain a substrate in which a red pixel pattern composed of a cured product of the radiation sensitive composition is arranged in a predetermined arrangement.

The post-baking conditions are preferably about 180 to 230 ° C for about 20 to 40 minutes.

The thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Also, by using a green-sensitive (A) colorant containing a green color The composition, and repeating the above processes (1) to (4), forming a green pixel pattern on the same substrate, and further using a blue radiation-sensitive linear composition containing a blue (A) colorant, and repeating the above (1) In the process of (4), a blue pixel pattern is formed on the same substrate, and a pixel array in which three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the pixel pattern forming order of each color can be arbitrarily selected.

A black matrix can be formed by using the green radiation-sensitive linear composition containing black (A) colorant and performing the above processes (1) to (4).

Color filter

The color filter of the present invention has a pixel and/or a black matrix formed by the radiation sensitive composition of the present invention and formed as described above.

Color liquid crystal display element

The color liquid crystal display element of the present invention includes the color filter of the present invention.

On the color filter formed as described above, a protective film is formed as necessary, and then a transparent conductive film is formed by sputtering. Examples of the transparent conductive film include an ITO film composed of indium oxide-tin oxide, an IZO film composed of indium oxide-zinc oxide, and the like. Since the cross-sectional shape of the pixel pattern formed using the radiation sensitive composition of the present invention is a forward tapered shape, the transparent electrode is not broken. Moreover, since the taper angle is not too flat, the edge of the pixel does not have a portion where the film thickness is thinned. Therefore, it is possible to manufacture a high-quality color liquid crystal display element having excellent electrical characteristics and chromaticity characteristics.

Further, in one embodiment of the color liquid crystal display device of the present invention, the luminescent layer forming composition for coloring layer of the present invention is used, and the film is formed on the film. On the panel array, by forming pixels and/or black matrices as described above, it is possible to manufacture a color liquid crystal display element having particularly excellent characteristics.

[Examples]

Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples.

Modulation of the pigment dispersion.

Modulation example 1

20 parts by weight of CI Pigment Red 254/CI Pigment Red 177/CI Pigment Yellow 150=20/70/10 (by weight) mixture was used as (A) colorant, 5 parts by weight (in terms of solid content) Disperbyk-2001 (BYK - Chemie Japan Co., Ltd. was prepared as a dispersant, and propylene glycol monomethyl ether acetate was used as a solvent so that the solid content concentration was 25%, and the pigment dispersion liquid (R1) was prepared by treatment using a bead disperser.

Modulation example 2

20 parts by weight of CI Pigment Red 254 was used as (A) coloring agent, and 5 parts by weight (in terms of solid content) Disperbyk-2001 (produced by BYK-Chemie Japan Co., Ltd. as a dispersing agent, and propylene glycol was used in such a manner that the solid content concentration was 25%). The methyl ether acetate was used as a solvent and treated with a bead disperser to prepare a pigment dispersion (R2).

Modulation example 3

20 parts by weight of CI Pigment Red 254/CI Pigment Red 242/CI Pigment Yellow 139=30/60/10 (by weight) mixture was used as (A) colorant, 5 parts by weight (in terms of solid content) Disperbyk-2001 (BYK -Chemie Japan produces a dispersant and uses C in a solid concentration of 25%. The pigment dispersion (R3) was prepared by treating the diol monomethyl ether acetate as a solvent and using a bead disperser.

Modulation example 4

20 parts by weight of CI Pigment Green 36/CI Pigment Yellow 150=50/50 (by weight) mixture was used as (A) colorant, and 5 parts by weight (calculated as solid content) Disperbyk-2001 (produced by BYK-Chemie Japan Co., Ltd. The pigment dispersion liquid (G1) was prepared by treating with a bead disperser using propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration was 25%.

Modulation example 5

20 parts by weight of CI Pigment Green 58/CI Pigment Yellow 150=60/40 (by weight) mixture was used as (A) colorant, and 5 parts by weight (in terms of solid content) Disperbyk-2001 (discreted by BYK-Chemie Japan Co., Ltd.) The pigment dispersion liquid (G2) was prepared by treating with a bead disperser using propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration was 25%.

Modulation example 6

20 parts by weight of CI Pigment Green 36/CI Pigment Yellow 150=60/40 (by weight) mixture was used as (A) colorant, and 5 parts by weight (in terms of solid content) Disperbyk-2001 (discreted by BYK-Chemie Japan Co., Ltd.) The pigment dispersion liquid (G3) was prepared by treating with a bead disperser using propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration was 25%.

Modulation example 7

20 parts by weight of CI Pigment Blue 15:6 was used as (A) coloring agent, and 5 parts by weight (in terms of solid content) Disperbyk-2001 (produced by BYK-Chemie Japan Co., Ltd. as a dispersing agent, and used as a solid content concentration of 25%) The pigment dispersion (B1) was prepared by treating propylene glycol monomethyl ether acetate as a solvent and using a bead disperser.

Modulation example 8

20 parts by weight of CI Pigment Blue 15:6/CI Pigment Violet 23=80/20 (by weight) mixture was used as (A) colorant, and 5 parts by weight (calculated as solid content) Disperbyk-2001 (BYK-Chemie Japan Co., Ltd.) The dispersant was prepared by using a propylene glycol monomethyl ether acetate as a solvent so as to have a solid content concentration of 25%, and treating it with a bead disperser to prepare a pigment dispersion liquid (B2).

Modulation example 9

20 parts by weight of CI Pigment Blue 15:6/CI Pigment Violet 23=60/40 (by weight) mixture was used as (A) colorant, and 5 parts by weight (in terms of solid content) Disperbyk-2001 (BYK-Chemie Japan Co., Ltd.) The dispersant was prepared by using a propylene glycol monomethyl ether acetate as a solvent so as to have a solid content concentration of 25%, and treating it with a bead disperser to prepare a pigment dispersion liquid (B3).

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 added to a flask equipped with a cooling tube and a stirrer, followed by adding 15 parts by weight of methacrylic acid, 35 parts by weight. Benzyl methacrylate, 19 parts by weight of N-phenyl maleimide, 10 parts by weight of glycerol methacrylate, 11 parts by weight of styrene, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 5 parts by weight of 2,4 - Diphenyl-4-methyl-1-pentene (chain transfer agent) and substituted with nitrogen. Subsequently, polymerization was carried out by slowly stirring and raising the temperature of the reaction solution to 80 ° C, and maintaining the temperature for 3 hours to obtain a copolymer solution. The obtained resin was Mw = 11,000, Mn = 5,000, and solid content concentration = 33.0%. This copolymer was referred to as "alkali-soluble resin (B-1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 153 parts by weight of propylene glycol monomethyl ether acetate, 15 parts by weight of methacrylic acid, 35 parts by weight of benzyl methacrylate, and 11 parts by weight of N-phenylbutylene were added.醯imine, 20 parts by weight of 2-acryloxyethyl succinic acid, 19 parts by weight of styrene, and 5 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (chain transfer agent), Next, a solution obtained by dissolving 3 parts by weight of 2,2'-azobisisobutyronitrile in 47 parts by weight of propylene glycol monomethyl ether acetate was added and substituted with nitrogen. Subsequently, the temperature of the reaction solution was slowly stirred and raised to 80 ° C, and after the polymerization was carried out for 4 hours at this temperature, 0.5 parts by weight of 2,2'-azobisisobutyronitrile was dissolved in 9.5 parts by weight. A solution of propylene glycol monomethyl ether acetate was further polymerized by raising the temperature of the reaction solution to 100 ° C and maintaining the temperature for 1 hour to obtain a copolymer solution. The obtained resin was Mw = 10,000, Mn = 6,000, and solid content concentration = 30.0%. This copolymer was referred to as "alkali-soluble resin (B-2)".

Synthesis Example 3

5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by adding 15 parts by weight of methacrylic acid, 35 parts by weight. Benzyl methacrylate, 25 parts by weight of N-phenyl maleimide, 10 parts by weight of glycerol methacrylate, 15 parts by weight of styrene and 7.5 parts by weight of 2,4-diphenyl-4- Methyl-1-pentene (chain transfer agent) and substituted with nitrogen. Subsequently, polymerization was carried out by slowly stirring and raising the temperature of the reaction solution to 80 ° C, and maintaining the temperature for 3 hours to obtain a copolymer solution. The obtained resin was Mw = 7,000, Mn = 3,500, and solid content concentration = 32.0%. This copolymer was referred to as "alkali-soluble resin (B-3)".

Example 1

100 parts by weight of the pigment dispersion liquid (R1) and 10 parts by weight of the alkali-soluble resin (A-1) as (B) alkali-soluble resin and 15 parts by weight of KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd. (in the formula (1), m =1, the number of groups represented by the formula (2) = 6 compounds) / dipentaerythritol hexaacrylate = 50 / 50 (by weight) mixture as (C) polyfunctional monomer, 5 parts by weight 2 -benzyl-2-dimethylamino-1-(4-morpholinephenyl)butan-1-one (manufactured by CIBA SPECIALTY CHEMICALS, trade name IRGACURE 369) as (D) photopolymerization initiator and solid content The liquid composition (S-1) was prepared by mixing propylene glycol monomethyl ether acetate as a solvent at a concentration of 25% by weight.

The liquid composition (S-1) was evaluated in the following order. The evaluation results are shown in Table 2.

Sensitivity evaluation

The liquid composition (S-1) was applied onto the surface of the glass substrate by a spin coater, and then prebaked for 4 minutes using a hot plate at 90 ° C to form a coating film having a film thickness of 1.3 μm. Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to light at a exposure amount of 400 J/m ² using a high pressure mercury lamp and passing through a photomask. Subsequently, the coating film on the substrate was sprayed and developed by spraying a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C at a development pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) for 60 seconds. Post-baking was carried out at 220 ° C for 30 minutes to form a dot pattern of 200 x 200 microns.

The dot pattern on the obtained pattern was formed on the obtained pattern, and the film thickness was measured by observation using a scanning electron microscope, and the residual film ratio (film thickness after post-baking × 100 / 1.3) was calculated. The degree of residual film rate is high and the sensitivity is good.

Adhesion evaluation

The liquid composition (S-1) was applied onto the surface of the glass substrate by a spin coater, and then prebaked for 4 minutes using a hot plate at 90 ° C to form a coating film having a film thickness of 1.3 μm. Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to light at a exposure amount of 400 J/m ² using a high pressure mercury lamp and passing through a photomask. Subsequently, the coating film on the substrate was sprayed and developed by spraying a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C at a development pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) for 60 seconds. Post-baking was carried out at 220 ° C for 30 minutes.

Next, the cured film was cross-cut into 100 checkerboard shapes in accordance with JIS K5400 specifications to evaluate adhesion. Further, when the checkerboard was not peeled off, it was evaluated as ○, and when 1 to 10 peeled off in the checkerboard, it was evaluated as Δ, and when the checkerboard peeled off more than 10, it was ×.

Evaluation of profile shape and imaging tolerance

The liquid composition (S-1) was applied onto the surface of the glass substrate by a spin coater, and then prebaked for 4 minutes using a hot plate at 90 ° C to form a coating film having a film thickness of 1.3 μm. Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to light at a exposure amount of 400 J/m ² using a high pressure mercury lamp and passing through a photomask. Subsequently, the coating film on the substrate was subjected to spray development by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C at a development pressure of 1.5 kgf/cm ² (nozzle diameter: 1 mm) for 60 seconds. Further, post-baking was carried out at 220 ° C for 30 minutes to form a stripe-shaped pixel pattern of 90 μm on the substrate.

Next, the obtained striped pixel pattern was observed using an optical microscope, and it was observed whether or not the edge of the pattern was defective.

Further, the obtained pixel pattern was observed using a scanning electron microscope (SEM), and the taper angle shown in Fig. 1 was measured. When the taper angle is 80 degrees or more, the transparent electrode film may be broken. On the other hand, when the taper angle is 20 degrees or less, the inclined portion of the pixel pattern becomes long, so that a portion where the film thickness is thinned at the edge of the pixel. The ideal cone angle is 30 to 70 degrees.

Examples 2 to 12 and Comparative Examples 1 to 11

The liquid compositions (S-2) to (S-23) were prepared in the same manner as in Example 1 except that the kinds and amounts of the respective components of the liquid composition were as shown in Table 1.

Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (S-2) to (S-23) were used instead of the liquid composition (S-1). The results are shown in Table 2.

In Table 1, each component is as follows.

C-1: dipentaerythritol hexaacrylate

C-2: pentaerythritol tetramethacrylate

C-3: In the above formulas (1) to (3), m = 1, the number of groups represented by the formula (2) = 6, and R ¹ is a compound in which all hydrogen atoms (trade name KAYARAD DPCA-60, Japan) Chemical company)

C-4: In the above formulas (1) to (3), m = 2, the number of groups represented by the formula (2) = 6, and R ¹ is a compound in which all hydrogen atoms (trade name KAYARAD DPCA-120, Japan) Chemical company)

C-5: In the above formulas (1) to (3), m = 1, the number of groups represented by the formula (2) = 2, and R ¹ is a compound in which all of them are hydrogen atoms (trade name KAYARAD DPCA-20, Japan) Chemical company)

C-6: In the above formulas (1) to (3), m = 1, the number of groups represented by the formula (2) = 3, and R ¹ is a compound in which all of them are hydrogen atoms (trade name KAYARAD DPCA-30, Japan) Chemical company)

D-1: 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)butan-1-one (trade name: IRGACURE 369, manufactured by CIBA SPECIALTY CHEMICALS)

D-2: 2-methyl-1-[4-methylthio)phenyl]-2-morpholinepropan-1-one (trade name: IRGACURE 907, manufactured by CIBA SPECIALTY CHEMICALS)

D-3: 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidine) (trade name) IRGACURE OXE02, CIBA SPECIALTY CHEMICALS company)

D-4: 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-diimidazole

D-5: 4,4'-bis(diethylamino)diphenyl ketone

D-6: 2-Hexylthiobenzothiazole

From Table 2, it is known that a compound containing 100 to 300 parts by weight of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is used as a coloring of a polyfunctional monomer with respect to 100 parts by weight of the alkali-soluble resin. When the layer-forming radiation sensitive composition was used (Examples 1 to 12), it was possible to form an ideal tapered shape and to have excellent adhesion.

On the other hand, when a compound having no caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is used as the polyfunctional monomer (Comparative Examples 8 and 11), the pixel pattern is reversely tapered. In addition, when the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is less than 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (Comparative Examples 1, 2, 4 to 7, 9 and 10), the ideal smooth shape cannot be formed, and at the same time, the pattern is defective. On the other hand, when it is more than 300 parts by weight (Comparative Example 3), the adhesion is deteriorated.

Fig. 1 is a schematic view showing a sectional shape of a pixel pattern.

Claims (8)

A radiation sensitive composition for forming a coloring layer, comprising: (A) a coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator; a radiation-linear composition containing 100 to 300 parts by weight of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule as (C) polyfunctionality with respect to 100 parts by weight of the (B) alkali-soluble resin The compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is a compound represented by the following formula (1). In the formula, all of the six R systems are groups represented by the following formula (2), or one to five of the six R groups are groups represented by the following formula (2), and the remainder is the following formula (3) The base shown, In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bonding hand. In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a dangling bond. The sensitizing radioactive composition for forming a color layer according to the first aspect of the invention, wherein the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is 6 in the above formula (1). All of R are compounds of the group represented by the above formula (2). The sensitizing radioactive composition for forming a color layer according to claim 1 or 2, further comprising a compound having two or more polymerizable unsaturated bonds having no caprolactone structure as (C) a polyfunctional single body. The sensitizing radiation-forming composition for forming a color layer according to claim 1 or 2, which is used for forming a composition of a coloring layer using an exposure amount of 800 J/m ² or less. The sensitizing radioactive composition for forming a color layer according to item 3 of the patent application is used for forming a composition of a coloring layer using an exposure amount of 800 J/m ² or less. A color filter comprising a coloring layer formed using the radiation sensitive composition for coloring layer formation according to any one of claims 1 to 5. A color liquid crystal display element comprising a color filter as in claim 6 of the patent application. A method for producing a color filter comprising the use of a radiation-sensitive composition for forming a color layer according to any one of claims 1 to 5, and using an exposure amount of 800 J/m ² or less to form a color. Layer process.