JP5182360B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display element. The present invention relates to a radiation-sensitive composition used for forming a colored layer, a color filter having a colored layer formed from the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

  As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (for example, patent documents) 1 and 2) are known.

In the technical field of color filters in recent years, in addition to reducing the exposure amount and shortening the tact time, in order to meet the demand for high color purity for color liquid crystal display elements, The content ratio of the pigment in the radiation-sensitive composition tends to be higher. As described above, when the content ratio of the pigment in the colored radiation-sensitive composition increases and the exposure amount when forming the pixel pattern decreases, the cross-sectional shape of the pixel pattern tends to be inversely tapered (overhang). is there. As a result, a problem that a transparent electrode such as ITO formed on the pixel pattern is broken has become apparent.
For example, Patent Documents 3 and 4 propose using a composition containing a chain transfer agent to solve the problem that the cross-sectional shape of the pixel pattern is inversely tapered. However, with such a technique, it has been difficult to form a pixel pattern with sufficient remaining film ratio and adhesion when the exposure amount is low. In addition, even if the cross-sectional shape is a forward taper, if the taper angle is too gentle, the inclined portion of the pixel pattern becomes long and a portion where the film thickness becomes thin at the edge of the pixel occurs, and the desired color cannot be reproduced. stay up.
Furthermore, in the mass production process of color filters, the problem of foreign matter and color unevenness generated in various processes congesting the inspection process and lowering the production efficiency has become apparent.

Prior art documents

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

The present invention has been made based on the circumstances as described above, and the problem is to form a pixel having an appropriate forward taper shape and excellent residual film ratio and adhesion even at a low exposure amount. The object is to provide a novel radiation-sensitive composition for forming a colored layer.
Furthermore, the objective of this invention is providing the color liquid crystal display element which comprises the color filter provided with the pixel formed from this radiation sensitive composition for coloring layer formation, and the said color filter.

  In view of such circumstances, the present inventors have conducted intensive research, and as a polyfunctional monomer, contain a specific amount of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule. The present inventors have found that a radiation-sensitive composition for forming a colored layer can solve the above-mentioned problems.

  That is, the present invention is a radiation-sensitive composition for forming a colored layer comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. And (C) a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule as a polyfunctional monomer (B) 100 to 300 wt. The present invention provides a radiation-sensitive composition for forming a colored layer, characterized by containing a part thereof.

  The present invention also provides a color filter comprising pixels formed using the radiation-sensitive composition, and a color liquid crystal display device comprising the color filter.

According to the radiation-sensitive composition of the present invention, in addition to reducing the exposure amount and shortening the tact time, even if the content ratio of the pigment in the colored radiation-sensitive composition is high, it has an appropriate forward tapered shape and A pixel pattern having excellent residual film ratio and adhesion can be formed. Furthermore, according to the radiation-sensitive composition of the present invention, a color filter can be produced with high production efficiency.
Therefore, the radiation-sensitive composition of the present invention can be used very suitably for the production of color filters for various uses such as color filters for color liquid crystal display elements in the electronic industry field, color imaging tube elements, color sensors and the like. it can.

It is a schematic diagram which shows the cross-sectional shape of a pixel pattern.

BEST MODE FOR CARRYING OUT THE INVENTION

The radiation-sensitive composition for forming a colored layer The “colored layer” in the radiation-sensitive composition for forming a colored layer of the present invention (hereinafter sometimes simply referred to as “radiation-sensitive composition”) is used for a color filter. Means a layer composed of pixels and / or black matrix.
Hereafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

-(A) Colorant-
The colorant (A) in the present invention is not particularly limited and may be either an organic pigment or an inorganic pigment.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists), specifically, the color index (CI) as described below. Listed are numbers.

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

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

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

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

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

  Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

These colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include polymers described in JP-A-8-259876, various commercially available polymers or oligomers for dispersing pigments, and the like. The polymer coating method on the carbon black surface is disclosed in, for example, JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like.
The colorants can be used alone or in admixture 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, (A) the coloring agent has high color development and high heat resistance. An agent, particularly a colorant having high heat decomposition resistance is preferable, specifically an organic colorant is preferable, and an organic pigment is particularly preferably used.
On the other hand, when the radiation-sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have light shielding properties, an organic pigment or carbon black is preferably used as the colorant (A).

  The radiation-sensitive composition of the present invention has an appropriate forward taper shape and a remaining film ratio even when the content of the colorant is 30% by weight or more in the total solid content of the radiation-sensitive composition. And a pixel having excellent adhesion can be formed. In the present invention, the content of the colorant is preferably 70% by weight or less, particularly preferably 60% by weight or less in the total solid content of the radiation-sensitive composition from the viewpoint of ensuring developability. Here, solid content is components other than the solvent mentioned later.

The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired.
As the dispersant, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, an alkylammonium salt or a phosphate ester salt of a polymer copolymer, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

  Such a dispersant is commercially available. For example, as a modified acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.), Cation Solspers 24000 (manufactured by Lubrizol Co., Ltd.), Ajisper PB821, Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) It can be mentioned.

  These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving developability and the like. It is -70 weight part, Most preferably, it is 10-50 weight part.

  Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative. Specific examples include a copper phthalocyanine derivative.

-(B) Alkali-soluble resin-
The (B) alkali-soluble resin contained in the radiation-sensitive composition of the present invention is particularly limited as long as it is soluble in the alkali developer used in the development processing step when forming the colored layer. Although not intended, it is usually a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among these, those containing a polymer having a carboxyl group are preferred, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing unsaturated monomer”). Copolymers (hereinafter referred to as “carboxyl group-containing copolymers”) with other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “copolymerizable unsaturated monomers”) are preferred. . In the present specification, (meth) acrylic acid refers to methacrylic acid or acrylic acid.

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
In the present invention, the carboxyl group-containing unsaturated monomer is preferably (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, Particularly preferred is (meth) acrylic acid.
These carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

Examples of the copolymerizable unsaturated monomer include:
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- N-substituted maleimides such as succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinyl Phenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether , Aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-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, methoxypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Unsaturated carboxylic acid esters such as glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, 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, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  In the present invention, as the copolymerizable unsaturated monomer, N-substituted maleimide, aromatic vinyl compound, unsaturated carboxylic acid ester, and macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain Those containing at least one selected from the group consisting of N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-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, Paracumi Preferred are those containing at least one selected from the group consisting of ethylene oxide-modified (meth) acrylates of ruphenol, polystyrene macromonomers, polymethylmethacrylate macromonomers, particularly N-phenylmaleimide, N-cyclohexylmaleimide, styrene, Ethylene oxide modification (meta) of α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, and paracumylphenol ) It preferably contains at least one selected from the group consisting of acrylates.

  In the present invention, for example, an alkali-soluble resin obtained by copolymerization of a copolymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is added to an alkali-soluble resin such as 2- (meth) acryloyloxyethyl isocyanate. By reacting the saturated isocyanate compound, a polymerizable unsaturated bond can be introduced into the side chain of the 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 an alkali developer tends to decrease, while if too large, the solubility in an alkali developer becomes excessive, and development with an alkali developer In this case, the pixel tends to drop off from the substrate and the film surface of the pixel is likely to be rough.

The weight average molecular weight in terms of polystyrene (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 it is 3,000-20,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.
Further, the number average molecular weight in terms of polystyrene (hereinafter also referred to as “Mn”) 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.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 4.0.

  The alkali-soluble resin in the present invention can be produced by a known method. For example, it is disclosed in JP 2003-222717 A, JP 2006-259680 A, WO 07/029871 pamphlet, and the like. The structure, Mw, and Mw / Mn can also be controlled by the existing method.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
In the present invention, the content of the (B) alkali-soluble resin is usually preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. If the content of the alkali-soluble resin is too small, for example, the alkali developability may decrease, or a residue or background stain may occur on the unexposed portion of the substrate or the light shielding layer. Further, since the colorant concentration decreases, it may be difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-
The polyfunctional monomer in the present invention comprises a monomer having two or more polymerizable unsaturated bonds, and a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule (hereinafter, "Sometimes referred to as a caprolactone structure-containing polyfunctional monomer") is contained in an amount of 100 to 300 parts by weight, preferably 100 to 250 parts by weight, based on 100 parts by weight of the (B) alkali-soluble resin. If the content of the caprolactone-modified polyfunctional monomer is less than 100 parts by weight, the desired effect may be impaired, while if it exceeds 300 parts by weight, the adhesion to the substrate may be reduced.

  Examples of the polyfunctional monomer containing a caprolactone structure include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and the like. Ε-caprolactone structure-containing polyfunctional (meth) acrylate obtained by esterifying (poly) alcohol with (meth) acrylic acid and ε-caprolactone. Among these, a caprolactone structure-containing polyfunctional monomer represented by the following formula (1) is preferable from the viewpoint that a moderately forward tapered pixel can be formed even at a low exposure amount.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

Of the compounds represented by the formula (1), those having 2 or more groups are preferred, those having 3 or more groups are more preferred, and compounds having 6 groups are particularly preferred.
Such a caprolactone structure-containing polyfunctional monomer is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3), Number of groups represented by formula (2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (formula, m = 1, number of groups represented by formula (2) = 3, Compound in which R ¹ is all hydrogen atoms), DPCA-60 (formula, m = 1, number of groups represented by formula (2) = 6, compound in which R ¹ is all hydrogen atoms), DPCA-120 (In the formula, m = 2, the number of groups represented by formula (2) = 6, and compounds in which R ¹ is all hydrogen atoms).
In the present invention, the caprolactone structure-containing polyfunctional monomer can be used alone or in admixture of two or more.

In the present invention, it is preferable to use another polyfunctional monomer together with the caprolactone structure-containing polyfunctional monomer from the viewpoint of increasing the remaining film ratio, and in particular, two or more having no caprolactone structure. It is preferable to use together with a compound having a polymerizable unsaturated bond.
Other polyfunctional monomers include, 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 the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone;
Examples thereof include tris [2- (meth) acryloyloxyethyl] phosphate and isocyanuric acid ethylene oxide-modified triacrylate.

Among these other polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane triacrylate. Methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, pentaerythritol triacrylate Monoesterified product of tosuccinic acid, monoester of pentaerythritol trimethacrylate and succinic acid Preferred are stearic compounds, monoesterified products of dipentaerythritol pentaacrylate and succinic acid, monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, and particularly trimethylolpropane triacrylate, pentaerythritol triacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol hexaacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, and the surface of the colored layer is smooth. It is preferable in that it has excellent properties and hardly causes scumming or film residue on the unexposed substrate and the light shielding layer.
The other polyfunctional monomers can be used alone or in admixture of two or more.

  The content of (C) the total polyfunctional monomer in the present invention is preferably 100 to 400 parts by weight, more preferably 100 to 300 parts by weight, with respect to 100 parts by weight of the (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 the total content is too large, for example, alkali developability may be deteriorated, soiling or filming may occur on the unexposed substrate or on the light shielding layer. There is a tendency for the rest to occur easily.

  In addition, the content ratio of the caprolactone structure-containing polyfunctional monomer in the (C) total polyfunctional monomer is preferably 25 to 100% by weight, and more preferably 50 to 75% by weight. By using the caprolactone structure-containing polyfunctional monomer in such a content ratio, it is possible to form an appropriately forward tapered pixel even at a low exposure amount.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] ester of acid, mono (meth) acrylate of polymer having carboxy group and hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate, N- (meth) acryloyl In addition to morpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam and the like, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more. The content ratio of the monofunctional monomer is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. If the content of the monofunctional monomer is too large, the strength and surface smoothness of the resulting colored layer may be insufficient.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization of the body.
Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like can be mentioned.

  In the present invention, the photopolymerization initiators can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, thioxanthone compounds, acetophenone compounds, biimidazole compounds, It is preferable to contain at least one selected from the group of triazine compounds and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

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

  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, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole 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, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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 the present invention, when a photo radical generator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  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. If the content of the photopolymerization initiator is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. There is a tendency that the colored layer is easily removed from the substrate during development.

-Additives-
Although the radiation sensitive composition of this invention contains the said (A)-(D) component, it can also contain another additive as needed.
Examples of other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, and anionic surfactants. Surfactants such as 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-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyl Adhesion promoters such as methoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Anticoagulants such as sodium polyacrylate; alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

-Solvent-
The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components and the additive component as necessary, but usually contains a solvent and is a liquid composition. It is prepared as a product.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as 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, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 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 Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 -Other esters such as ethyl oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid - propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along 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, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method, for example, it can be prepared by mixing the components (A) to (D) together with a solvent and additives, In a solvent, in the presence of a dispersing agent and, if necessary, a dispersing aid to be added, optionally with a part of the component (B), for example, using a bead mill, a roll mill, etc. It is preferable to prepare a pigment dispersion by adding and mixing the components (B) to (D) and, if necessary, additional solvent or additive.

-Color filter formation method-
Next, a method for forming the color filter of the present invention using the radiation-sensitive composition of the present invention will be described.
The method for forming a color filter usually includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) A step of post-baking the developed coating film.
Hereinafter, these steps will be sequentially described.

(1) Step First, on the surface of the substrate, if necessary, a light shielding layer (black matrix) is formed so as to divide a portion where pixels are formed, and, for example, red (A) is formed on the substrate. The radiation-sensitive composition of the present invention containing a colorant is usually applied as a liquid composition and then pre-baked to remove the solvent by evaporation to form a coating film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition to the substrate, an appropriate coating method such as a spin coating method, a casting coating method, a roll coating method, or a coating method using a slit die coater can be employed. A coating method using a slit die coater is preferred.
The prebaking condition is usually about 2 to 4 minutes at 70 to 110 ° C. In addition, according to the radiation sensitive composition of this invention, a pixel and a black matrix can be formed even if a prebaking process is omitted.
The coating thickness is usually 1.0 to 10 μm, preferably 1.0 to 6.0 μm, particularly preferably 1.0 to 4.0 μm as the film thickness after removal of the solvent.

(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 the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is usually 10~10,000J / ^{m 2.} According to the radiation-sensitive composition of the present invention, a pixel having an appropriate forward taper shape with an exposure amount of 800 J / m ² or less, and even an exposure amount of 600 J / m ² or less, and excellent in remaining film ratio and adhesion. Can be formed. The lower limit of the exposure amount is preferably 200 J / m ² or more from the viewpoint of controllability when a light source with high illuminance is used.

(3) Process Then, it develops using a developing solution, Preferably an alkali developing solution, The unexposed part of a coating film is dissolved and removed.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably about 10 to 300 seconds at room temperature.

-(4) Process-
Thereafter, a post-baked coating film after development can provide a substrate on which red pixel patterns made of a cured product of the radiation-sensitive composition are arranged in a predetermined arrangement.
The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Moreover, a green pixel pattern is formed on the same board | substrate by repeating the said (1)-(4) process using the green radiation sensitive composition containing a green (A) coloring agent, and also blue. (A) Using the blue radiation-sensitive composition containing the colorant, the steps (1) to (4) are repeated to form a blue pixel pattern on the same substrate, whereby red, green A pixel array in which pixel patterns of three primary colors of blue and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.
A black matrix can be formed by performing the steps (1) to (4) using a green radiation-sensitive composition containing a black colorant (A).

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

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
On the color filter formed as described above, after forming a protective film as necessary, a transparent conductive film is formed by sputtering. Examples of the transparent conductive film include an ITO film made of indium oxide-tin oxide, an IZO film made 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 taper, the transparent electrode does not break. Further, since the taper angle is not too gentle, a portion where the film thickness is reduced does not occur at the edge of the pixel. Therefore, a high-quality color liquid crystal display element having excellent electrical characteristics and chromaticity characteristics can be manufactured.
Further, as one form of the color liquid crystal display element of the present invention, a pixel and / or a black matrix is formed as described above on the thin film transistor substrate array using the radiation-sensitive composition for forming a colored layer of the present invention. By doing so, a color liquid crystal display element having particularly excellent characteristics can be produced.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Preparation 1 of pigment dispersion
(A) C.I. I. Pigment red 254 / C.I. I. Pigment red 177 / C.I. I. Pigment Yellow 150 = 20/70/10 (weight ratio) 20 parts by weight of a mixture, Disperbyk-2001 (by BYK) as a dispersant (5 parts by weight) (solid content conversion), and propylene glycol monomethyl ether acetate as a solvent A pigment dispersion (R1) was prepared by processing with a bead mill using a solid content of 25%.

Preparation Example 2
(A) C.I. I. 20 parts by weight of Pigment Red 254, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 25% Then, a pigment dispersion (R2) was prepared by treatment with a bead mill.

Preparation Example 3
(A) C.I. I. Pigment red 254 / C.I. I. Pigment red 242 / C.I. I. CI Pigment Yellow 139 = 30/60/10 (weight ratio) 20 parts by weight of the mixture, Dispersbyk-2001 (produced by BYK) as a dispersant (5 parts by weight) (solid content conversion), and propylene glycol monomethyl ether acetate as a solvent A pigment dispersion (R3) was prepared by processing with a bead mill using a solid content concentration of 25%.

Preparation Example 4
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 50/50 (weight ratio) 20 parts by weight of the mixture, Disperbyk-2001 (by BYK) as a dispersant (5 parts by weight) (solid content), and propylene glycol monomethyl ether acetate as the solvent A pigment dispersion (G1) was prepared by treating with a bead mill using a concentration of 25%.

Preparation Example 5
(A) C.I. I. Pigment green 58 / C.I. I. Pigment Yellow 150 = 60/40 (weight ratio) 20 parts by weight of the mixture, Disperbyk-2001 (by BYK) as a dispersant (5 parts by weight) (solid content), and propylene glycol monomethyl ether acetate as the solvent as a solid content A pigment dispersion (G2) was prepared by using a bead mill with a concentration of 25%.

Preparation Example 6
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 60/40 (weight ratio) 20 parts by weight of the mixture, Disperbyk-2001 (by BYK) as a dispersant (5 parts by weight) (solid content), and propylene glycol monomethyl ether acetate as the solvent as a solid content A pigment dispersion (G3) was prepared by using a bead mill with a concentration of 25%.

Preparation Example 7
(A) C.I. I. 20 parts by weight of Pigment Blue 15: 6, 5 parts by weight of Disperbyk-2001 (produced by BYK) as a dispersant (solid content conversion), and a solid content concentration of 25% of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (B1) was prepared by processing with a bead mill.

Preparation Example 8
(A) C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 20 parts by weight of 80/20 (weight ratio) mixture, Disperbyk-2001 (by BYK) (dispersed as a dispersant) as 5 parts by weight (solid content conversion), and propylene glycol monomethyl ether acetate as a solvent as a solid content A pigment dispersion (B2) was prepared by using a bead mill with a concentration of 25%.

Preparation Example 9
(A) C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 60/40 (weight ratio) 20 parts by weight of a mixture, Disperbyk-2001 (by BYK) (dispersed as a dispersant) as 5 parts by weight (in terms of solid content), and propylene glycol monomethyl ether acetate as a solvent as a solid content A pigment dispersion (B3) was prepared by using a bead mill with a concentration of 25%.

Synthesis synthesis example 1 of alkali-soluble resin
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid, 35 parts by weight of benzyl methacrylate, N -19 parts by weight of phenylmaleimide, 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) Parts were charged and purged with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours for polymerization to obtain a copolymer solution. The obtained resin had Mw = 11,000, Mn = 5,000, and solid content concentration = 33.0%. This copolymer is referred to as “alkali-soluble resin (B-1)”.

Synthesis example 2
In a flask equipped with a condenser 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, 11 parts by weight of N-phenylmaleimide, 20 parts by weight of 2-acryloyloxyethyl 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, and then 3 parts by weight of 2,2′-azobisisobutyronitrile was added to propylene glycol. A solution dissolved in 47 parts by weight of monomethyl ether acetate was charged and purged with nitrogen. The mixture was then gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 4 hours for polymerization. Then, 0.5 part by weight of 2,2′-azobisisobutyronitrile was added to propylene glycol monomethyl. A solution dissolved in 9.5 parts by weight of ether acetate was charged, and then the temperature of the reaction solution was raised to 100 ° C., and this temperature was maintained for 1 hour for further polymerization to obtain a copolymer solution. The obtained resin had Mw = 10,000, Mn = 6,000, and solid content concentration = 30.0%. This copolymer is referred to as “alkali-soluble resin (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid, 35 parts by weight of benzyl methacrylate, N -25 parts by weight of 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) were charged and purged with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours for polymerization to obtain a copolymer solution. The obtained resin had Mw = 7,000, Mn = 3,500, and solid content concentration = 32.0%. This copolymer is referred to as “alkali-soluble resin (B-3)”.

Example 1
100 parts by weight of the pigment dispersion (R1), (B) 10 parts by weight of alkali-soluble resin (A-1) as the alkali-soluble resin (in terms of solid content), and (C) KAYARAD manufactured by Nippon Kayaku Co., Ltd. as the polyfunctional monomer DPCA-60 (a compound in which m = 1, the number of groups represented by formula (2) = 6 in formula (1)) / dipentaerythritol hexaacrylate = 50/50 (weight ratio) 15 parts by weight of a mixture, (D) 5 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, Then, a liquid composition (S-1) was prepared by mixing propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration was 25% by weight.

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

Evaluation of sensitivity The liquid composition (S-1) was applied on the surface of a glass substrate using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. Formed. Subsequently, after cooling this board | substrate to room temperature, it exposed with the exposure amount of 400 J / m < ² > through the photomask to the coating film on a board | substrate using a high pressure mercury lamp. Then, after performing shower development by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds, Post-baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm dot pattern.
The dot pattern on the substrate obtained in the formation of the pattern was observed with a scanning electron microscope and the film thickness was measured to calculate the remaining film ratio (film thickness after post-baking × 100 / 1.3). It can be said that the higher the remaining film ratio, the better the sensitivity.

Evaluation of adhesion The liquid composition (S-1) was applied on the surface of a glass substrate using a spin coater and then pre-baked on a hot plate at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. Formed. Subsequently, after cooling this board | substrate to room temperature, it exposed with the exposure amount of 400 J / m < ² > to the coating film on a board | substrate using the high pressure mercury lamp. Thereafter, a 0.04 wt% aqueous potassium hydroxide solution at 23 ° C. was discharged for 60 seconds at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and then shower development was performed. Post-baked for a minute.
Next, according to the JIS K5400 standard, the cured film was cross-cut into 100 grids to evaluate adhesion. Then, the case where the grid was not peeled off was evaluated as ◯, the case where 1-10 pieces of the grid were peeled off was evaluated as Δ, and the case where the grids were peeled off more than 10 was evaluated as x.

Evaluation of cross-sectional shape and development resistance The liquid composition (S-1) was applied on the surface of a glass substrate using a spin coater and then pre-baked on a hot plate at 90 ° C. for 4 minutes. A 3 μm coating film was formed. Subsequently, after cooling this board | substrate to room temperature, it exposed with the exposure amount of 400 J / m < ² > through the photomask to the coating film on a board | substrate using a high pressure mercury lamp. Thereafter, shower development was performed by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a development pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds. Next, post-baking was performed at 220 ° C. for 30 minutes to form a 90 μm stripe pixel pattern on the substrate.
Next, the obtained stripe pixel pattern was observed with an optical microscope, and the presence or absence of pattern edge chipping was observed.
Furthermore, the cross-sectional shape of the obtained pixel pattern was observed with a scanning electron microscope (SEM), and the taper angle shown in FIG. 1 was measured. If the taper angle is 80 degrees or more, the 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 a portion where the film thickness becomes thin occurs at the edge of the pixel. The ideal taper angle is 30 to 70 degrees.

Examples 2-12 and Comparative Examples 1-11
Liquid compositions (S-2) to (S-23) were prepared in the same manner as in Example 1 except that the types and amounts of each component of the liquid composition were as shown in Table 1.
Subsequently, 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 formula (2) = 6, R ¹ compounds wherein all hydrogen atoms (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)
C-4: a compound in which m = 2 in the above formulas (1) to (3), the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms (trade name KAYARAD DPCA-120, Japan (Made by Kayaku)
C-5: a compound in which m = 1 in the above formulas (1) to (3), the number of groups represented by formula (2) = 2, and R ¹ is all hydrogen atoms (trade name KAYARAD DPCA-20, Japan (Made by Kayaku)
C-6: a compound in which m = 1 in the above formulas (1) to (3), the number of groups represented by formula (2) = 3, and R ¹ is all hydrogen atoms (trade name KAYARAD DPCA-30, Japan (Made by Kayaku)
D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
D-3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name Irgacure OXE02, Ciba Specialty・ Made by 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, as a polyfunctional monomer, 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 the molecule with respect to 100 parts by weight of the alkali-soluble resin. When the forming radiation-sensitive composition is used (Examples 1 to 12), it can be seen that an ideal forward tapered shape is formed and the adhesiveness is excellent.
On the other hand, when a polyfunctional monomer that does not contain a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule (Comparative Examples 8 and 11), the pixel pattern has an inverse taper. It turns out that it becomes a shape. Further, 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 with respect to 100 parts by weight of the alkali-soluble resin (Comparative Examples 1, 2, 4). -7, 9 and 10), an ideal forward tapered shape cannot be formed, and chipping may occur in the pixel pattern. On the other hand, when it exceeds 300 parts by weight (Comparative Example 3), it is understood that the adhesion is poor. .

Claims (8)

  A radiation-sensitive composition for forming a colored layer, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (C) The polyfunctional monomer contains 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. A radiation-sensitive composition for forming a colored layer. 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 formula (1).

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)   The compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is a compound in which all six Rs in the formula (1) are groups represented by the formula (2). The radiation sensitive composition for colored layer formation of Claim 2.   (C) The colored layer formation according to any one of claims 1 to 3, further comprising a compound having no caprolactone structure and having two or more polymerizable unsaturated bonds as a polyfunctional monomer. Radiation sensitive composition. The radiation-sensitive composition for forming a colored layer according to any one of claims 1 to 4, which is a composition for forming a colored layer at an exposure dose 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 of any one of Claims 1-5.   A color liquid crystal display device comprising the color filter according to claim 6. The manufacturing method of a color filter including the process of forming a colored layer with the exposure amount of 800 J / m < ² > or less using the radiation sensitive composition for colored layer formation of any one of Claims 1-5.

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