KR20100108621A - Radiation-sensitive composition for the formation of colored layers, color filters, and color liquid crystal displays - Google Patents

Abstract

This invention provides the radiation sensitive composition for colored layer formation which can form the pixel excellent also in residual film rate and adhesiveness in a suitable taper shape as a low exposure amount. Moreover, as a radiation sensitive composition for colored layer formation containing (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (C) polyfunctional monomer is a molecule | numerator The radiation sensitive composition for colored layer formation containing 100-300 weight part of compounds which have a caprolactone structure and two or more polymerizable unsaturated bonds with respect to 100 weight part of (B) alkali-soluble resins is contained.

Description

Radiation-sensitive composition, color filter and color liquid crystal display element for colored layer formation {RADIATION-SENSITIVE COMPOSITION FOR THE FORMATION OF COLORED LAYERS, COLOR FILTERS, AND COLOR LIQUID CRYSTAL DISPLAYS}

The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device, and more particularly, to a color layer useful for a color filter used in a transmissive or reflective color liquid crystal display device, a color image tube device, or the like. The radiation sensitive composition used for formation, the color filter which has a colored layer formed from this radiation sensitive composition, and the color liquid crystal display element provided with this color filter.

A method of forming a color filter using a colored radiation-sensitive composition, wherein a coating film of a colored radiation-sensitive composition is formed on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance, and a photomask having a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as "exposure"), developing, dissolving and removing unexposed portions, and then post-baking (see Patent Documents 1 and 2, for example). This is known.

In recent years, in the technical field of color filters, it has become mainstream to reduce the exposure time and shorten the tact time. In addition, in order to meet the demand for high color purity for color liquid crystal display devices, the content of pigments in the colored radiation-sensitive composition is included. The ratio tends to be higher and higher. Thus, when the content rate of the pigment which occupies in a coloring radiation sensitive composition becomes high and the exposure amount at the time of forming a pixel pattern becomes small, there exists a tendency for the cross-sectional shape of a pixel pattern to become a reverse taper (overhang). As a result, the problem that the transparent electrode, such as ITO formed on a pixel pattern, disconnects is present.

For the problem that the cross-sectional shape of the pixel pattern becomes an inverse taper, for example, Patent Documents 3 and 4 propose using a composition containing a chain transfer agent. However, in such a technique, when the exposure amount decreases, it is difficult to form a pixel pattern with sufficient residual film rate and adhesion. In addition, even if the cross-sectional shape is a forward taper, if the taper angle is too slow, the inclined portion of the pixel pattern becomes long, resulting in a portion where the film thickness becomes thin at the edge of the pixel, resulting in a problem that the desired color cannot be reproduced.

In addition, in the mass production process of color filters, foreign matters, color irregularities, and the like, which occur in various processes, stagnate the inspection process to reduce the production efficiency.

Japanese Patent Laid-Open No. 2-144502 Japanese Patent Laid-Open No. 3-53201 Japanese Patent Publication No. 2002-167404 Japanese Patent Publication No. 2002-287337

SUMMARY OF THE INVENTION The present invention has been made on the basis of the above circumstances, and its problem is to provide a novel radiation-sensitive composition for forming a colored layer which can form a pixel having excellent residual film ratio and adhesiveness in an appropriate forward taper shape even with a low exposure amount. Is in.

Moreover, the objective of this invention is providing the color filter which comprises the pixel formed from the radiation sensitive composition for colored layer formation, and the color liquid crystal display element provided with this color filter.

In view of such circumstances, the present inventors earnestly studied, and as a multifunctional monomer, the radiation-sensitive composition for forming a colored layer containing a specific amount of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is described above. The present invention was found to be able to solve the problem.

That is, this invention is a radiation sensitive composition for colored layer formation containing (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (C) polyfunctional monomer A radiation sensitive composition for forming a colored layer, comprising 100 to 300 parts by weight of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in a molecule (B) based on 100 parts by weight of an alkali-soluble resin. To provide.

Moreover, this invention also provides the color filter which comprises the pixel formed using the said radiation sensitive composition, and the color liquid crystal display element provided with the said color filter.

According to the radiation-sensitive composition of the present invention, in addition to reducing the exposure amount to shorten the tact time, even if the content ratio of the pigment in the colored radiation-sensitive composition is high, an appropriate pure taper shape also forms a pixel pattern excellent in residual film ratio and adhesion. can do. Moreover, according to the radiation sensitive composition of this invention, a color filter can be manufactured with high production efficiency.

Therefore, the radiation sensitive composition of this invention can be used very favorably for manufacture of the color filter of various uses, such as a color image sensor element, a color sensor, in addition to the color filter for color liquid crystal display elements in the electronic industry.

1 is a schematic diagram showing a cross-sectional shape of a pixel pattern.

Radiation-sensitive composition for colored layer formation

The "colored layer" in the radiation sensitive composition for forming a colored layer of the present invention (hereinafter may be simply referred to as a "radiation sensitive composition") is a layer containing a pixel and / or a black matrix used for a color filter. Means.

Hereinafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

-(A) colorant-

It does not specifically limit as (A) coloring agent in this invention, Any of an organic pigment and an inorganic pigment may be sufficient.

Examples of the organic pigments include compounds classified as pigments in color indices (issued by The Society of Dyers and Colorists, Inc.), and specifically those given the following color index (CI) numbers. have.

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

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

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

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

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 58;

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

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

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

Examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium, ultramarine blue, royal blue, and chromium oxide. And cobalt rust, amber, titanium black, synthetic iron black, carbon black and the like.

These colorants may be used by modifying their particle surface with a polymer, if desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, the polymer for various pigment dispersions, and oligomer etc. which are marketed are mentioned, for example. About the polymer coating method of the carbon black surface, it is disclosed by Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc., for example. It is.

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

In the case where the radiation-sensitive composition of the present invention is used for formation of a pixel, since the pixel requires high color development and heat resistance, the (A) colorant is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance. Specifically, an organic colorant is preferable, and an organic pigment is especially used preferably.

On the other hand, when the radiation sensitive composition of this invention is used for formation of a black matrix, since a light shielding property is calculated | required by a black matrix, organic pigment or carbon black is used suitably as (A) coloring agent.

The radiation sensitive composition of the present invention can form a pixel having an appropriate forward taper shape and excellent residual film ratio and adhesion even when the content of the colorant is 30% by weight or more in the total solid of the radiation sensitive composition. In addition, in this invention, content of a coloring agent is 70 weight% or less in total solids of a radiation sensitive composition from a viewpoint of ensuring developability, Preferably it is 60 weight% or less. Here, solid content is components other than the solvent mentioned later.

The coloring agent in this invention can be used together with a dispersing agent and a dispersal auxiliary agent if desired.

As the dispersant, suitable dispersants such as cationic, anionic, nonionic, amphoteric and the like can be used, but a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, acrylic copolymer, polyurethane, polyester, alkylammonium salt or phosphate ester salt of a high molecular copolymer, cationic comb graft polymer, etc. are mentioned. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branch polymers are graft-bonded to one molecule of a stem polymer having a plurality of basic groups (cationic functional groups), and for example, the stem polymer moiety is polyethylenimine or eggplant. The polymer comprised from the ring-opening polymer whose polymer part is epsilon -caprolactone is mentioned. Of these dispersants, modified acrylic copolymers, polyurethanes, and cationic comb graft polymers are preferred.

Such dispersants are commercially available, for example, as modified acrylic copolymers, such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), and polyurethanes. Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Corporation), Solsperth 76500 (manufactured by Lubrizol Co., Ltd.), cationic Examples of the comb graft polymer include Solsper 24000 (manufactured by Lubrizol Co., Ltd.), Azisper PB821, and Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.).

These dispersants can be used individually or in mixture of 2 or more types. Since content of a dispersing agent improves developability etc., it is 100 weight part or less normally with respect to 100 weight part of (A) coloring agents, Preferably it is 0.5-100 weight part, More preferably, it is 1-70 weight part, Especially Preferably it is 10-50 weight part.

As said dispersing adjuvant, a blue pigment derivative, a yellow pigment derivative, etc. are mentioned, for example, Specifically, a copper phthalocyanine derivative etc. are mentioned, for example.

-(B) alkali-soluble resin-

The alkali-soluble resin (B) contained in the radiation-sensitive composition of the present invention is not particularly limited as long as it has solubility with respect to the alkaline developer used in the development step in forming the colored layer, but is usually carboxyl group or phenolic. It is a polymer which has acidic functional groups, such as a hydroxyl group. Especially, it is preferable to contain the polymer which has a carboxyl group, and especially the ethylenically unsaturated monomer which can copolymerize another ethylenically unsaturated monomer (henceforth "carboxyl group-containing unsaturated monomer") which has one or more carboxyl groups (henceforth "in air" And a copolymer (hereinafter referred to as "carboxyl group-containing copolymer") are preferred. In addition, in this specification, (meth) acrylic acid represents methacrylic acid or acrylic acid.

As a carboxyl group-containing unsaturated monomer, for example

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

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

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

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

In the present invention, as the carboxyl group-containing unsaturated monomer, (meth) acrylic acid, monosuccinic acid [2- (meth) acryloyloxyethyl],? -Carboxypolycaprolactone mono (meth) acrylate, and the like are preferable, and in particular (meth) Acrylic acid is preferred.

These carboxyl group-containing unsaturated monomers can be used individually or in mixture of 2 or more types.

As the copolymerizable unsaturated monomer, for example,

N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3 -Maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (acridy N-position substituted maleimide, such as nil) maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, aromatic vinyl compounds such as m-vinylbenzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol ( Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropyl Lenglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- Unsaturated carboxyl such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol Acid esters;

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

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

Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

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

In the present invention, the copolymerizable unsaturated monomer is selected from the group consisting of an N-position substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain. It is preferable to contain 1 or more types, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, (alpha) -methylstyrene, p-hydroxy- (alpha) -methylstyrene, methyl (meth) acrylate, n -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate , 4-hydroxyphenyl (meth) acrylate, group consisting of ethylene oxide modified (meth) acrylate of paracumylphenol, polystyrene macromonomer, polymethyl methacrylate macromonomer It is preferable to contain 1 or more types selected from these, Especially N-phenylmaleimide, N-cyclohexyl maleimide, styrene, (alpha) -methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, Containing at least one member selected from the group consisting of 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, and ethylene oxide modified (meth) acrylate of paracumylphenol It is preferable.

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

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the copolymerization ratio is too small, the solubility of the resulting radiation-sensitive composition in the alkali developer tends to decrease. On the other hand, when the copolymerization ratio is too high, the solubility in the alkaline developer becomes excessive, and when developing with the alkali developer, the substrate of the pixel It tends to be easy to cause dropout from the film or roughness of the pixel surface.

The polystyrene reduced weight average molecular weight (hereinafter also referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 1,000 to 45,000, preferably 3,000 to 20,000. If Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical characteristics may be deteriorated. If the Mw is too large, the resolution is reduced or the pattern shape is damaged, Moreover, there exists a possibility that a dry foreign material may arise easily at the time of application | coating by a slit nozzle system.

In addition, the polystyrene reduced number average molecular weight (henceforth "Mn") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin in this invention is 1,000-45,000 normally, Preferably Preferably 3,000 to 20,000.

Moreover, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin in this invention becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-4.0.

Although alkali-soluble resin in this invention can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Publication No. 07/029871. The structure, Mw, and Mw / Mn can also be controlled by the method disclosed in these.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

In this invention, 10-1,000 mass parts is preferable normally with respect to 100 mass parts of (A) coloring agents, and, as for content of (B) alkali-soluble resin, 20-500 mass parts is especially preferable. If the content of the alkali-soluble resin is too small, for example, alkali developability may decrease, or residues or ground contamination may occur on the substrate or the light shielding layer of the unexposed portion, and when too large, the colorant concentration decreases relatively. Therefore, it is difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-

The polyfunctional monomer in this invention contains the monomer which has a 2 or more polymerizable unsaturated bond, and has a caprolactone structure and 2 or more polymerizable unsaturated bonds in a molecule ("caprolactone structure containing polyfunctional monomer" May be 100 to 300 parts by weight, and preferably 100 to 250 parts by weight based on 100 parts by weight of the (B) alkali-soluble resin. If content of a caprolactone modified polyfunctional monomer is less than 100 weight part, there exists a possibility that a desired effect may be impaired, and when it exceeds 300 weight part, there exists a possibility that adhesiveness to a board | substrate may fall.

Examples of caprolactone structure-containing polyfunctional monomers include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethyl. (Epsilon) -caprolactone structure containing polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols, such as olmelamine, and (meth) acrylic acid and (epsilon) -caprolactone. Especially, the caprolactone structure containing polyfunctional monomer represented by following General formula (1) is preferable at the point which can form the pixel of an appropriate forward taper shape also as a low exposure amount.

(In the formula, all 6 R is a group represented by the following formula (2), or 1 to 5 of the six R is a group represented by the formula (2), the rest is a group represented by the formula (3)

(In formula, R <^1> represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and it shows that "*" is a bond.)

(In formula, R <^1> represents a hydrogen atom or a methyl group, and it shows that "*" is a bond.)

It is preferable that the group represented by Formula (2) is two or more among the compound represented by the said Formula (1), It is more preferable that it is three or more, The compound of six is especially preferable.

Such caprolactone structure-containing polyfunctional monomers are commercially available as, for example, KAYARAD DPCA series from Nippon Kayaku Co., Ltd. Number = 2, a compound in which R ¹ is all a hydrogen atom), DPCA-30 (the number of groups represented by the above formulas 1 to 3, m = 1, formula 2 = 3, a compound in which R ¹ is all hydrogen atoms), DPCA -60 (the above formulas 1 to 3, m = 1, the number of groups represented by the formula (2) = 6, R ¹ are all hydrogen atoms), DPCA-120 (m = 2 in the above formulas 1 to 3, formula The number of groups represented by 2 = 6, the compound in which all of R ¹ are hydrogen atoms), and the like.

In this invention, a caprolactone structure containing polyfunctional monomer can be used individually or in mixture of 2 or more types.

In the present invention, from the viewpoint of increasing the residual film ratio, it is preferable to use another polyfunctional monomer together with the caprolactone structure-containing polyfunctional monomer, and in particular, a compound having two or more polymerizable unsaturated bonds without a caprolactone structure; It is preferable to use together.

As another polyfunctional monomer, for example

Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;

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

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

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

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

Tris [2- (meth) acryloyloxyethyl] phosphate, an isocyanuric acid ethylene oxide modified triacrylate, etc. are mentioned.

Among these other polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylic Laterate, dipentaerythritol hexamethacrylate, monoester of pentaerythritol triacrylate and succinic acid, monoester of pentaerythritol trimethacrylate and succinic acid, dipentaerythritol pentaacrylate and succinic acid Monoester, dipentaerythritol pentametha Monoesters of acrylate and succinic acid are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacryl Monoesters of the rate and succinic acid and monoesters of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the substrate and the light shielding layer of the unexposed part. It is preferable in that it is difficult to generate background contamination, film residue, and the like.

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

Content of the (C) all polyfunctional monomer in this invention becomes like this. Preferably it is 100-400 weight part, More preferably, it is 100-300 weight part with respect to 100 weight part of (B) alkali-soluble resin. If the total content is too small, the desired effect of the present invention may be impaired. On the other hand, if too much, alkali developability is lowered, for example, background contamination on the substrate or the light shielding layer of the unexposed portion, film residue, and the like. This tends to be easy to occur.

Moreover, the content rate of the caprolactone structure containing polyfunctional monomer in all the (C) polyfunctional monomers becomes like this. Preferably it is 25-100 weight%, More preferably, it is 50-75 weight%. By using a caprolactone structure containing polyfunctional monomer in such a content ratio, the pixel of an appropriate forward taper shape can be formed also as a low exposure amount.

In addition, in this invention, a part of polyfunctional monomer can also be replaced by the monofunctional monomer which has one polymerizable unsaturated bond.

As said monofunctional monomer, mono [of bivalent or more polyvalent carboxylic acids, such as monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl], for example, Mono (meth) acrylate, N- (meth) acryloyl, of a polymer having a carboxyl group and a hydroxyl group at both ends, such as (meth) acryloyloxyalkyl] ester and ω-carboxypolycaprolactone mono (meth) acrylate In addition to morpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam and the like, M-5600 (trade name, manufactured by Toagosei Co., Ltd.), etc. may be mentioned as a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types. The content rate of a monofunctional monomer is 90 weight% or less normally with respect to the sum total of a polyfunctional monomer and a monofunctional monomer, Preferably it is 50 weight% or less. When there are too many content rates of a monofunctional monomer, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

-(D) photoinitiator-

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

As such a photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, (alpha)-diketone type compound, a multinuclear quinone type compound, a xanthone type compound, a diazo type compound, an imide sulfonate type compound, etc. are mentioned.

Although the photoinitiator can be used individually or in mixture of 2 or more types, as a photoinitiator in this invention, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, and a triazine type It is preferable to contain 1 or more types chosen from a compound and an O-acyl oxime type compound group.

As a specific example of a thioxanthone type compound among the preferable photoinitiators in this invention, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thi Orcanthone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

Specific examples of the acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Further, specific examples of the biimidazole compound include 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 etc. are mentioned.

Moreover, when using a biimidazole type compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (di Amine hydrogen donors, such as ethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof, but the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may further improve sensitivity. It is preferable at the point.

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

In addition, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

In this invention, when using radical radicals other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, content of a photoinitiator is 0.01-120 weight part normally with respect to 100 weight part of (C) polyfunctional monomers, Preferably it is 1-100 weight part. When there is too little content of a photoinitiator, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined | prescribed arrangement, and when too many, when the formed colored layer develops It tends to be easy to drop off from the substrate.

-additive-

Although the radiation sensitive composition of this invention contains the said (A)-(D) component, it may further contain other additive as needed.

As another additive here, For example, fillers, such as glass and an alumina; Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate) s; Surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors such as sodium polyacrylate; And alkali solubility improving agents such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

-menstruum-

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

As said solvent, as long as it does disperse | distribute or melt | dissolve or melt | dissolve the component (A)-(D) and additive component which comprise a radiation sensitive composition, and does not react with these components, it can select suitably and can use.

As such a solvent, for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as 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 ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

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

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n- formic acid Amyl, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid i-propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 Other esters such as ethyl oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

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

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3-methoxybutyl acetate in terms of solubility, pigment dispersibility, and coating properties. , Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxy propionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionic acid Ethyl, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n -Butyl, ethyl pyruvate, etc. are preferable.

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

Furthermore, with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate And high boiling point solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

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

Although content of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition is 5-50 weight% normally, Preferably it is 10-40. The amount which becomes weight% is preferable.

In the present invention, the radiation-sensitive composition can be produced by a suitable method, and for example, can be produced by mixing the components (A) to (D) with a solvent or an additive, but the pigment is dispersed in a solvent, And in the presence of a dispersing aid added as needed, optionally with a part of component (B), for example, using a bead mill, a roll mill, etc., mixing and dispersing while grinding to obtain a pigment dispersion (B). It is preferable to manufacture by adding and mixing (D) component (D) with further solvent and additive as needed.

Formation method of color filter

Next, the method of forming the color filter of this invention using the radiation sensitive composition of this invention is demonstrated.

The method of forming a color filter normally includes the process of following (1)-(4) at least.

(1) Process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate.

(2) The process of exposing to at least one part of the said coating film.

(3) The process of developing the coating film after exposure.

(4) The process of post-baking the coating film after image development.

Hereinafter, these processes are demonstrated one by one.

(1) process

First, as needed, the light-shielding layer (black matrix) is formed so that the part which forms a pixel may be divided on the surface of a board | substrate, and the radiation of the present invention which contains a red (A) colorant, for example on this board | substrate. The coating composition is usually formed by applying the composition as a liquid composition, followed by prebaking and evaporation of the solvent.

As a board | substrate used at this process, a ring-opening polymer of cyclic olefin, its hydrogenated substance, etc. other than glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyether sulfone are mentioned, for example. have.

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

When applying a liquid composition to a board | substrate, the appropriate coating methods, such as a spin coating method, the flexible coating method, the roll coating method, and the coating method using a slit die coater, can be employ | adopted, but the spin coating method and the coating method using a slit die coater are employ | adopted. desirable.

The conditions of prebaking are about 2 to 4 minutes at 70-110 degreeC normally. In addition, according to the radiation sensitive composition of the present invention, the pixel and the black matrix can be formed even if the preliminary baking step is omitted.

The coating thickness is a film thickness after removal of the solvent, which is usually 1.0 to 10 m, preferably 1.0 to 6.0 m, and particularly preferably 1.0 to 4.0 m.

(2) process

Then, it exposes to at least one part of the formed coating film. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern.

As radiation used for exposure, visible light, an ultraviolet-ray, an ultraviolet ray, an electron beam, X-rays, etc. can be used, for example, but the radiation in the range whose wavelength is 190-450 nm is preferable.

The exposure amount of radiation is 10-100,000 J / m <2> normally. According to the radiation sensitive composition of this invention, even if it is an exposure amount of 800 J / m <2> or less, and the exposure amount of 600 J / m <2> or less, a suitable taper shape and excellent residual film rate and adhesiveness can be formed. Moreover, it is preferable that the minimum of exposure amount is 200 J / m <2> or more from a controllability viewpoint at the time of using the light source with high illuminance.

(3) process

Then, it develops using a developing solution, Preferably alkaline developing solution, and removes and removes the unexposed part of a coating film.

Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabi, and the like. Aqueous solutions, such as cyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method and the like can be applied.

As for image development conditions, about 10 to 300 second is preferable at normal temperature.

(4) process

Subsequently, by post-baking the coating film after development, the board | substrate with which the red pixel pattern containing the hardened | cured material of a radiation sensitive composition was arrange | positioned in a predetermined | prescribed arrangement can be obtained.

As for the post-baking conditions, about 20 to 40 minutes are preferable at 180-230 degreeC.

The film thickness of the pixel formed in this way is 0.5-5.0 micrometers normally, Preferably it is 1.0-3.0 micrometers.

In addition, by repeating the above steps (1) to (4) using a green radiation-sensitive composition containing a green (A) colorant, a green pixel pattern is formed on the same substrate, and a blue ( A) By repeating the above steps (1) to (4) using a blue radiation-sensitive composition containing a colorant, a blue pixel pattern is formed on the same substrate, thereby red, green, and blue pixels of three primary colors. A pixel array in which patterns are arranged in a predetermined array can be formed on a substrate. However, the formation order of the pixel pattern of each color can be arbitrarily selected.

A black matrix can be formed by performing said process (1)-(4) using the green radiation sensitive composition containing black (A) coloring agent.

Color filter

The color filter of this invention has the pixel and / or black matrix formed as mentioned above from the radiation sensitive composition of this invention.

Color liquid crystal display element

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

On the color filter formed as mentioned above, after forming a protective film as needed, a transparent conductive film is formed by sputtering. Examples of the transparent conductive film include an ITO film containing indium oxide-tin oxide, an IZO film containing indium oxide-zinc oxide, and the like. Since the cross-sectional shape of the pixel pattern formed using the radiation sensitive composition of this invention is a forward taper, a transparent electrode does not disconnect. In addition, since the taper angle is not too gentle, there is no case where the film thickness becomes thin at the edge of the pixel. Therefore, the high quality color liquid crystal display element excellent in the electrical characteristic and chromaticity characteristic can be manufactured.

Moreover, as one form of the color liquid crystal display element of this invention, using the radiation sensitive composition for colored layer formation of this invention, a pixel and / or a black matrix are formed on a thin film transistor substrate array as mentioned above. Thereby, the color liquid crystal display element which has especially excellent characteristic can be manufactured.

&Lt; Example 1 >

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

Preparation of Pigment Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 177 / C.I. Pigment Yellow 150 = 20/70/10 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solids), and propylene glycol monomethyl ether acetate as a solvent. It was used so that solid content concentration might be 25%, it processed by the bead mill, and the pigment dispersion liquid (R1) was produced.

Production Example 2

(A) As a coloring agent, C.I. 20 parts by weight of Pigment Red 254, 5 parts by weight (in terms of solids) of Disperbyk-2001 (manufactured by BYK) as a dispersant, and propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration is 25%. , Bead mill, to prepare a pigment dispersion (R2).

Production Example 3

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 242 / C.I. Pigment Yellow 139 = 30/60/10 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solids), and propylene glycol monomethyl ether acetate as a solvent. It was used so that solid content concentration might be 25%, it processed by the bead mill, and the pigment dispersion liquid (R3) was produced.

Preparation Example 4

(A) As a coloring agent, C.I. Pigment Green 36 / C.I. Pigment Yellow 150 = 50/50 (weight ratio) 20 parts by weight of the mixture, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solids), and propylene glycol monomethyl ether acetate as the solvent. Was used to be 25%, and treated with a bead mill to prepare a pigment dispersion (G1).

Preparation Example 5

(A) As a coloring agent, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 = 60/40 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solids), and propylene glycol monomethyl ether acetate as a solvent. Was used to be 25%, and treated with a bead mill to prepare a pigment dispersion (G2).

Preparation Example 6

(A) As a coloring agent, C.I. Pigment Green 36 / C.I. Pigment Yellow 150 = 60/40 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solids), and propylene glycol monomethyl ether acetate as a solvent. Was used to be 25%, and treated with a bead mill to prepare a pigment dispersion (G3).

Preparation Example 7

(A) As a coloring agent, C.I. 20 parts by weight of Pigment Blue 15: 6, 5 parts by weight of Disperbyk-2001 (manufactured by BYK Co., Ltd.) as a dispersant (in terms of solids), and a propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration is 25%. It used and processed by the bead mill and manufactured the pigment dispersion (B1).

Preparation Example 8

(A) As a coloring agent, C.I. Pigment Blue 15: 6 / C.I. Pigment Violet 23 = 80/20 (weight ratio) 20 parts by weight of the mixture, 5 parts by weight (in terms of solids) of Disperbyk-2001 (manufactured by BYK Corporation) as a dispersant, and propylene glycol monomethyl ether acetate as the solvent. Was used to be 25%, and treated with a bead mill to prepare a pigment dispersion (B2).

Preparation Example 9

(A) As a coloring agent, C.I. Pigment Blue 15: 6 / C.I. Pigment Violet 23 = 60/40 (weight ratio) 20 parts by weight of a mixture, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solids), and propylene glycol monomethyl ether acetate as a solvent Was used to be 25%, and treated with a bead mill to prepare a pigment dispersion (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 15 parts by weight of methacrylic acid and benzyl methacrylate 35 Parts by weight, 19 parts by weight of N-phenylmaleimide, 10 parts by weight of glycerol methacrylate, 11 parts by weight of styrene, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 2,4-diphenyl-4-methyl- 5 parts by weight of 1-pentene (chain transfer agent) was added thereto, followed by nitrogen substitution. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 80 ° C, and the copolymer solution was obtained by maintaining the polymerization for 3 hours. Obtained resin was Mw = 11,000, Mn = 5,000 and solid content concentration = 33.0%. Let this copolymer be "alkali-soluble resin (B-1)."

Synthesis Example 2

153 parts by weight of propylene glycol monomethyl ether acetate, 15 parts by weight of methacrylic acid, 35 parts by weight of benzyl methacrylate, 11 parts by weight of N-phenylmaleimide, 2-acryloyloxyethyl in a flask equipped with a cooling tube and a stirrer 20 parts by weight of succinic acid, 19 parts by weight of styrene, and 5 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (chain transfer agent) were added, followed by 3 parts by weight of 2,2'-azobisisobutyronitrile. A solution dissolved in 47 parts by weight of propylene glycol monomethyl ether acetate was added thereto, followed by nitrogen substitution. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 80 ° C, the temperature was maintained for 4 hours, and the polymerization was carried out, followed by polymerization of 0.5 parts by weight of 2,2'-azobisisobutyronitrile at 9.5 weight of propylene glycol monomethyl ether acetate. The solution which melt | dissolved in the part was thrown in, and then the temperature of the reaction solution was raised to 100 degreeC, this temperature was hold | maintained for 1 hour, and also the superposition | polymerization was obtained. Obtained resin was Mw = 10,000, Mn = 6,000 and solid content concentration = 30.0%. Let this copolymer be "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 15 parts by weight of methacrylic acid and benzyl methacrylate 35 Parts by weight, 25 parts by weight of N-phenylmaleimide, 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), Nitrogen substitution. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 80 ° C, and the copolymer solution was obtained by maintaining the polymerization for 3 hours. Obtained resin was Mw = 7,000, Mn = 3,500 and solid content concentration = 32.0%. Let this copolymer be "alkali-soluble resin (B-3)."

Example 1

100 parts by weight of the pigment dispersion (R1), (B) 10 parts by weight of the alkali-soluble resin (A-1) as the alkali-soluble resin (in terms of solids), and (C) the polyfunctional monomer manufactured by KAYARAD DPCA-60 (Formula 1) 15 parts by weight of the mixture represented by m = 1, the number of groups represented by the formula (2) = / dipentaerythritol hexaacrylate = 50/50 (weight ratio), (D) 2-benzyl- as a photopolymerization initiator 5 parts by weight of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (available from Ciba Specialty Chemicals, trade name Irgacure 369), and propylene glycol monomethyl ether acetate as a solvent The liquid mixture was mixed so that the concentration might be 25% by weight to prepare a liquid composition (S-1).

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

Evaluation of sensitivity

After apply | coating a liquid composition (S-1) on the surface of a glass substrate using a spin coater, prebaking was performed for 4 minutes on the 90 degreeC hotplate, and the coating film of 1.3 micrometers in thickness was formed. Subsequently, after cooling this board | substrate to room temperature, it exposed by the exposure amount of 400 J / m <2> through the photomask using the high pressure mercury lamp to the coating film on the board | substrate. Thereafter, a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C. was discharged to a coating film on the substrate at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) for 60 seconds, after which a shower development was performed, followed by further 30 minutes at 220 ° C. Baking was performed to form a dot pattern of 200 x 200 m.

The residual film ratio (film thickness after post-baking x 100 / 1.3) was computed by observing the dot pattern on the board | substrate obtained in formation of the said pattern with the scanning electron microscope, and measuring a film thickness. The higher the residual film ratio, the better the sensitivity.

Adhesion Evaluation

After apply | coating a liquid composition (S-1) on the surface of a glass substrate using a spin coater, prebaking was performed for 4 minutes on the 90 degreeC hotplate, and the coating film of 1.3 micrometers in thickness was formed. Subsequently, after cooling this board | substrate to room temperature, it exposed to the coating film on a board | substrate by the exposure amount of 400 J / m <2> using the high pressure mercury lamp. Thereafter, a 0.04% by weight aqueous potassium hydroxide solution at 23 DEG C was discharged to the coating film at a developing pressure of 1 kgf / cm &lt; 2 &gt; (nozzle diameter of 1 mm) for 60 seconds, after which a shower development was performed, followed by post-baking at 220 DEG C for 30 minutes. Was performed.

Next, the cured film was cross-cut in 100 grid | lattices form according to JISK5400 standard, and adhesive evaluation was performed. (Circle) and the case where 1-10 pieces of a lattice are peeled as (circle) and the case where more than 10 lattice peels were evaluated as (x).

Evaluation of cross section shape and developing resistance

After apply | coating a liquid composition (S-1) on the surface of a glass substrate using a spin coater, prebaking was performed for 4 minutes on the 90 degreeC hotplate, and the coating film of 1.3 micrometers in thickness was formed. Subsequently, after cooling this board | substrate to room temperature, it exposed by the exposure amount of 400 J / m <2> through the photomask using the high pressure mercury lamp to the coating film on the board | substrate. Thereafter, shower development was performed by discharging a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C. for 60 seconds at a developing pressure of 1.5 kgf / cm 2 (nozzle diameter 1 mm) to the coating film on the substrate. Subsequently, post-baking was carried out at 220 ° C. for 30 minutes to form a 90 μm striped pixel pattern on the substrate.

Next, the obtained stripe pixel pattern was observed with the optical microscope, and the presence or absence of the defect of a pattern edge was observed.

Moreover, the cross-sectional shape of the obtained pixel pattern was observed with the scanning electron microscope (SEM), and the taper angle shown in FIG. 1 was measured. If this taper angle is 80 degrees or more, there exists a possibility that a transparent electrode film may be disconnected. On the other hand, when the taper angle is 20 degrees or less, the inclined portion of the pixel pattern becomes long, and the portion where the film thickness becomes thin at the edge of the pixel is generated. The ideal taper angle is 30 to 70 degrees.

Examples 2-12 and Comparative Examples 1-11

The liquid compositions (S-2) to (S-23) were prepared in the same manner as in Example 1 except that the kind and amount of each component of the liquid composition were as shown in Table 1.

Next, it evaluated similarly to Example 1 except having used liquid compositions (S-2)-(S-23) instead of liquid composition (S-1), respectively. 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: the compound of the formulas 1-3, m = 1, the number of groups represented by the formula (2) = 6, and R ¹ are all hydrogen atoms (trade names KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)

C-4: In the said Chemical Formulas 1-3, m = 2, the number of groups represented by Formula 2 = 6, and R <^1> are all hydrogen atoms (brand name KAYARAD DPCA-120, the Nippon Kayaku Co., Ltd. make).

C-5: In the above formulas 1 to 3, m = 1, the number of groups represented by the formula (2) = 2, and R ¹ are all hydrogen atoms (trade names KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.)

C-6: In the above Chemical Formulas 1 to 3, m = 1, the number of groups represented by the Chemical Formula 2 = 3, and R ¹ are all hydrogen atoms (trade names KAYARAD DPCA-30, manufactured by Nippon Kayaku Co., Ltd.)

D-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals, Inc.)

D-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals, Inc.)

D-3: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name Irgacure OXE02, Ciba ㆍ specialty chemicals)

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

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

D-6: 2-mercaptobenzothiazole

From Table 2, a radiation sensitive composition for forming a colored layer containing 100 to 300 parts by weight of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in a molecule as a polyfunctional monomer is used based on 100 parts by weight of an alkali-soluble resin. In the case (Examples 1-12), it turned out that an ideal forward taper shape is formed and it is excellent also in adhesiveness.

On the other hand, when the polyfunctional monomer was used without containing a compound having a caprolactone structure and two or more polymerizable unsaturated bonds (Comparative Examples 8 and 11), it was found that the pixel pattern became an inverse taper shape. . Further, if the content of the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is less than 100 parts by weight relative to 100 parts by weight of the alkali-soluble resin (Comparative Examples 1, 2, 4 to 7, 9 and 10), Not only did an ideal forward taper shape not be formed, but a defect might generate | occur | produce in a pixel pattern, and when 300 weight part exceeded (comparative example 3), it turned out that adhesiveness is inferior.

Claims (8)

(A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (C) polyfunctional monomer, which has a caprolactone structure and two or more polymerizable unsaturateds in a molecule 100-300 weight part of compounds which have a bond with respect to 100 weight part of (B) alkali-soluble resin are contained, The radiation sensitive composition for colored layer formation characterized by the above-mentioned. The radiation sensitive composition for forming a colored layer according to claim 1, wherein the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is a compound represented by the following general formula (1).
<Formula 1>

(In the formula, all 6 R is a group represented by the following formula (2), or 1 to 5 of the six R is a group represented by the formula (2), the rest is a group represented by the formula (3)
<Formula 2>

(In formula, R <^1> represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and it shows that "*" is a bond.)
<Formula 3>

(In formula, R <^1> represents a hydrogen atom or a methyl group, and it shows that "*" is a bond.) The persimmon for forming a colored layer according to claim 2, wherein the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is a compound of the group represented by the general formula (2) in which all six R's in the general formula (1) are used. Radioactive composition. The radiation sensitive for forming a colored layer according to any one of claims 1 to 3, further comprising (C) a polyfunctional monomer, which further contains a compound which does not have a caprolactone structure and has two or more polymerizable unsaturated bonds. Composition. The radiation sensitive composition for colored layer formation as described in any one of Claims 1-4 which is a composition for forming a colored layer by the exposure amount of 800 J / m <2> or less. The color filter provided with the colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-5. The color liquid crystal display element provided with the color filter of Claim 6. The manufacturing method of the color filter containing the process of forming a colored layer by exposure amount of 800 J / m <2> or less using the radiation sensitive composition for colored layer formation in any one of Claims 1-5.

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