JP2010262059A - Colored radiation-sensitive composition, color filter and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored radiation-sensitive composition for exposure by a YAG third-order harmonic wave laser (at a wavelength of 355 nm), the composition being suitable for manufacturing a color filter. <P>SOLUTION: The colored radiation-sensitive composition for exposure by a YAG third-order harmonic wave laser contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, wherein the (B) alkali-soluble resin contains a polymer having an acidic functional group and a polymerizable unsaturated group, and the (D) photopolymerization initiator contains a thioxanthone compound, at least one selected from a group consisting of compounds expressed by formula (1), and an O-acyl oxime compound. In formula (1), R<SP>1</SP>and R<SP>2</SP>each independently represent a 1-6C alkyl group, and R<SP>3</SP>represents a 1-6C alkyl group which may have a substituent, a 1-20C alkoxy group or dialkylaminophenyl group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored radiation-sensitive composition, a color filter, and a color liquid crystal display device, and more specifically, a colored radiation-sensitive composition suitable for production of a color filter by YAG third harmonic laser exposure, and the colored radiation-sensitive composition. The present invention relates to a color filter having a colored layer formed from a conductive composition, and a color liquid crystal display device including the color filter.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color having a desired pattern shape by irradiating a dry coating film with a radiation through a photomask (hereinafter referred to as “exposure”) and developing (see, for example, Patent Documents 1 and 2) It has been known.
In this exposure step, it is common to use an ultra-high pressure mercury lamp that emits ultraviolet light such as g-line or i-line as a light source, and to perform processing by a proximity exposure method.

  However, in the conventional proximity exposure system, (1) since the photomask tends to increase in size with the increase in the substrate size in recent years, the photomask fabrication requires a huge cost. (2) The photomask With the increase in size, there is a problem that a high-resolution pattern cannot be formed due to an increase in deflection and positioning error of the photomask. (3) In an exposure method using a conventional ultrahigh pressure mercury lamp as a light source, There is a problem in that there is a limit to shortening the takt time by reducing the exposure amount.

  On the other hand, a laser exposure method capable of forming a pattern without reducing the size of a photomask or without using a photomask has attracted attention, and a coloring composition suitable for manufacturing a color filter by the laser exposure has also been proposed. (For example, see Patent Documents 3 and 4).

By the way, the YAG laser is a laser having a wavelength of 1064 nm that oscillates when a rod obtained by doping neodymium ions or the like into YAG (a garnet structure crystal composed of a complex oxide of yttrium and aluminum) is excited by a laser diode or the like.
The YAG third harmonic laser is a laser whose short length is shortened to one third by passing the YAG laser through a wavelength conversion element made of a nonlinear crystal, and its wavelength is 355 nm.
So far, no coloring composition suitable for YAG third harmonic laser exposure has been reported.

JP-A-2-144502 JP-A-3-53201 Japanese Patent Laid-Open No. 9-73171 JP 2008-287213 A

  This invention is made | formed based on the above situations, The subject is providing the coloring radiation sensitive composition for YAG 3rd harmonic laser (wavelength 355nm) exposure suitable for manufacture of a color filter. is there.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using an alkali-soluble resin having a specific structure in combination with a specific photopolymerization initiator, and have completed the present invention. It was.

  That is, the present invention is a colored radiation-sensitive composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, B) The alkali-soluble resin contains a polymer having an acidic functional group and a polymerizable unsaturated group, and (D) the photopolymerization initiator is a thioxanthone compound and the following formula (1)

(In formula (1), R ¹ and R ² are, independently of each other, represents an alkyl group having 1 to 6 carbon atoms, R ³ is an optionally substituted alkyl group having 1 to 6 carbon atoms, C1-C20 alkoxy group or following formula (2)

(In the formula (2), R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, and “*” represents a bond.) . )
A colored radiation-sensitive composition for YAG third-harmonic laser exposure, comprising at least one selected from the group consisting of compounds represented by formula (1) and an O-acyloxime compound. .

  Moreover, this invention provides the color filter provided with the colored layer formed using said colored radiation-sensitive composition for YAG 3rd harmonic laser exposure.

  Moreover, this invention provides the color liquid crystal display element which comprises said color filter.

  The present invention also includes (1) a step of forming a coating film of the colored radiation-sensitive composition on a substrate, and (2) a step of exposing a YAG third harmonic laser to at least a part of the coating film. The manufacturing method of the color filter containing is also provided.

  According to the colored radiation-sensitive composition for YAG third harmonic laser exposure of the present invention, when a colored layer is formed by YAG third harmonic laser exposure, patterning characteristics such as pattern shape, remaining film ratio, linearity, etc. It is possible to form an excellent colored layer. Therefore, the colored radiation-sensitive composition for YAG third harmonic laser exposure of the present invention includes color filters for various uses such as color filters for color liquid crystal display elements, color image pickup tube elements, and color sensors. It can be used very suitably when producing by harmonic laser exposure.

Hereinafter, the present invention will be described in detail.
In the present specification, the “colored layer” means a layer composed of pixels and / or a black matrix used for a color filter.

Colored radiation-sensitive composition for YAG third-harmonic laser exposure Composition of colored radiation-sensitive composition for YAG third-harmonic laser exposure of the present invention (hereinafter sometimes simply referred to as “radiation-sensitive composition”). The components will be described.

-(A) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment. Since the color filter is required to have heat resistance, the colorant in the present invention is preferably 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 Dyers and Colorists), specifically, the following Color Index (C.I. ) Can be listed.

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 (III) oxide), 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 the formation of a pixel, since the pixel is required to have a high-definition color, (A) the colorant is preferably a colorant with high color developability. Organic pigments are 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).

  In the present invention, the content of (A) the colorant is preferably 5 to 70% by mass in the total solid content from the viewpoint of forming a pixel having excellent transparency and color purity or a black matrix having excellent light shielding properties. 5 to 60% by mass is more preferable. 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 alkyl ammonium salt or a phosphate ester salt of a polymer copolymer, a cationic graft polymer, and the like can be given. Here, the cationic graft polymer refers to a polymer having a structure in which two or more branch polymers are grafted to one molecule of a backbone polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which a part is polyethyleneimine and a branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethanes, and cationic graft polymers are preferable.

  Such a dispersant is commercially available. For example, as a modified acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN21116, BYK-LPN6919, BYK-LPN21324 (above, BYK Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol Co., Ltd.) Manufactured by Co., Ltd.), Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Azisper PB821, Azisper PB822, Per PB823, Adisper PB824, mention may be made of Ajisper PB827 (Ajinomoto Fine-Techno Co., Ltd.), and the like.

These dispersants can be used alone or in admixture of two or more. The content of the dispersant is preferably 100 parts by weight or less, more preferably 1 to 70 parts by weight, and particularly preferably 10 to 50 parts by weight with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving developability and the like.
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 in the present invention contains a polymer having an acidic functional group and a polymerizable unsaturated group, and the content is preferably 40% by mass or more, more preferably in the total alkali-soluble resin. Is 60% by mass or more. By including such an alkali-soluble resin, a colored layer having excellent pattern edge linearity can be formed.

Examples of the acidic functional group include a carboxyl group and a phenolic hydroxyl group, and a carboxyl group is preferred from the viewpoint of alkali solubility.
Examples of the polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, an allyl group, and the like, and a (meth) acryloyl group is preferable from the viewpoint of obtaining a desired effect. Moreover, it is preferable that the polymer which has an acidic functional group and a polymerizable unsaturated group has a polymerizable unsaturated group in the side chain.

The polymer having an acidic functional group and a polymerizable unsaturated group is not particularly limited as long as the above requirements are satisfied.
(B1) (b1) The polymerizable unsaturated compound having an oxiranyl group is 1 to 90 with respect to the carboxyl group of the monomer copolymer containing 5 to 60% by mass of the unsaturated carboxylic acid. A polymer obtained by reacting mol%,
(B2) (b1) 5 to 50% by mass of unsaturated carboxylic acid and (b3) 1 to 50% by mass of a polymerizable unsaturated compound having a hydroxyl group, based on the hydroxyl group of the monomer copolymer, (B4) a polymer obtained by reacting 30 to 100 mol% of a polymerizable unsaturated compound having an isocyanato group,
(B3) (b2) 70 to 100 of (b1) unsaturated carboxylic acid with respect to the oxiranyl group of the monomer copolymer containing 5 to 80% by mass of the polymerizable unsaturated compound having an oxiranyl group It may be at least one selected from the group consisting of polymers obtained by reacting mol% and further reacting (b5) 10 to 100 mol% of polybasic acid anhydride with the generated hydroxyl group.

  Specific examples of the (b1) unsaturated carboxylic acid include (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], As specific examples of the polymerizable unsaturated compound having (b2) oxiranyl group such as ω-carboxypolycaprolactone mono (meth) acrylate, glycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, 3, Specific examples of the polymerizable unsaturated compound (b3) having hydroxyl group (b3) such as 4-epoxycyclohexylmethyl (meth) acrylate, p-vinylbenzyl glycidyl ether and the like are 2-hydroxyethyl (meth) acrylate, 2,3- Dihydroxypropyl (meth) acrylate and the like (b4) isocyanato group Specific examples of the polymerizable unsaturated compound having 2- (meth) acryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl methacrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, etc. (B5) Specific examples of the polybasic acid anhydride include succinic anhydride, glutaric anhydride, phthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, and the like.

In the case of a polymer having an acidic functional group and a polymerizable unsaturated group, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, acenaphthylene, methyl (meth) acrylate, n- butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, isobornyl (meth Polymerizable unsaturated compounds such as acrylate, benzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and ethylene oxide-modified (meth) acrylate of paracumylphenol can be appropriately copolymerized.

  Specific examples of the polymer having an acidic functional group and a polymerizable unsaturated group include, for example, JP-A-5-19467, JP-A-6-230212, JP-A-8-262221, and JP-A-2008-181095. And polymers disclosed in Japanese Patent Publication No. Gazette.

  In the present invention, as the alkali-soluble resin, an alkali-soluble resin having no polymerizable unsaturated group can be used together with a polymer having an acidic functional group and a polymerizable unsaturated group. Specific examples of the alkali-soluble resin having no polymerizable unsaturated group include, for example, JP-A-7-140654, JP-A-10-31308, JP-A-10-300922, and JP-A-11-174224. Mention may be made of the copolymers disclosed in JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is 1,000 to 45,000, 000 to 30,000 is preferred. In this case, if Mw is too small, the remaining film rate of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, There is a possibility that the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.
In addition, the ratio (Mw / Mn) of Mw of the alkali-soluble resin in the present invention to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is , Preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

  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 alkali-soluble resin is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the colorant (A). In this case, if the content of the alkali-soluble resin is too small, for example, the alkali developability may be reduced, or a residue or background stain may occur on the unexposed portion of the substrate or on the light shielding layer. However, since the pigment concentration is relatively lowered, it may be difficult to achieve a target color concentration as a thin film.

-(C) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds, and preferably a monomer having 2 to 10 polymerizable unsaturated bonds. As such a 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 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 hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene;
Examples include tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide-modified triacrylate, poly (meth) acrylate having a urethane structure, poly (meth) acrylate having a caprolactone structure, and the like.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable, and poly (meth) acrylates of 3 to 7 polyhydric alcohols. And their dicarboxylic acid-modified products are more preferred. Specific examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, penta Erythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate Dipentaerythritol monoesterified with tosuccinic acid Preferred are monoesterified products of ethyl pentaacrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, particularly trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, diester Pentaerythritol hexaacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, monoesterified product of dipentaerythritol pentaacrylate and succinic acid has high strength of the colored layer, excellent surface smoothness of the colored layer, and This is preferable in that ground stains, film residue and the like are hardly generated on the unexposed substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The content of the polyfunctional monomer in the present invention is preferably 50 to 300 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin. By setting the content of the polyfunctional monomer in such a range, a colored layer excellent in strength, surface smoothness, and pattern edge linearity can be formed, and also excellent in alkali developability. A radiation sensitive composition can be obtained.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is a compound that generates an active species capable of initiating polymerization of the (C) polyfunctional monomer by exposure with a YAG third harmonic laser.
In this invention, a photoinitiator contains at least 1 sort (s) chosen from the group which consists of a thioxanthone type compound and the compound represented by said Formula (1), and containing an O-acyl oxime type compound, Their total content is preferably 20% by mass or more, more preferably 30% by mass or more in the total photopolymerization initiator. By using these photopolymerization initiators in combination with the specific alkali-soluble resin, when a colored layer is formed by YAG third harmonic laser exposure, a colored layer having excellent patterning characteristics can be formed. it can.

  As said thioxanthone type compound, the compound represented by following formula (3) can be mentioned, for example.

(In formula, R < ⁶ > -R < ⁹ > shows a hydrogen atom, a halogen atom, a C1-C18 alkyl group, or a C1-C18 alkoxy group mutually independently.)

In the above formula (3), R ⁶ and R ⁸ are preferably a hydrogen atom, and R ⁷ and R ⁹ are preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms. Furthermore, R ⁷ and R ⁹ are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
Specific examples of the thioxanthone compound represented by the above formula (3) 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 can be mentioned.
In the present invention, the thioxanthone compounds can be used alone or in admixture of two or more.

Moreover, in said Formula (1) and (2), as R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ >, a methyl group or an ethyl group is preferable. As a C1-C6 alkyl group of R < ³ >, a methyl group, an ethyl, or a propyl group is preferable, As a substituent, a C1-C6 alkoxy group is preferable. The alkoxy group having 1 to 20 carbon atoms of R ³ is preferably an alkoxy group having a chain or branched alkyl group having 1 to 8 carbon atoms.
Specific examples of the compound represented by the formula (1) include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-dimethylaminoacetophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-diethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-diethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate (n-butoxy) ethyl, ethyl 4-diethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, isoamyl 4-diethylaminobenzoate and the like.
In this invention, the compound represented by the said Formula (1) can be used individually or in mixture of 2 or more types.

The O-acyloxime compound is not particularly limited as long as it is a photopolymerization initiator having an acyloxime structure (> C═N—O—CO—). For example, International Publication No. WO2002 / 100903 No. pamphlet, International Publication No. 2006/018933 pamphlet, International Publication No. 2008/078678 pamphlet and the like. Specific examples of the O-acyloxime 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-tetrahydrofuranylmethoxybenzoyl) -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). In the present invention, the O-acyloxime compound is preferably a compound having a carbazole structure from the viewpoint of improving the linearity of the pattern edge.
In the present invention, the O-acyloxime compounds can be used alone or in admixture of two or more.

  Moreover, from the point which raises a desired effect more, the compounding mass ratio of at least 1 sort (s) chosen from the group which consists of a thioxanthone type compound and the compound represented by said Formula (1), and an O-acyl oxime type compound is 5 : 1 to 1:10, more preferably 2: 1 to 1: 5.

In the present invention, the linearity of the pattern edge can be further improved by using a biimidazole compound together with the above photopolymerization initiator. 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 ′, Examples include 5,5′-tetraphenyl-1,2′-biimidazole.
When a biimidazole compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor in combination. 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.
In the present invention, when a biimidazole compound is used, the content thereof is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass with respect to 100 parts by mass of the O-acyloxime compound. Further, the content of the hydrogen donor is preferably 10 to 100 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the biimidazole compound.

In the present invention,
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2 Acetophenone compounds such as-(4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one;
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 (trichloro Methyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (can also be used trichloromethyl) known photopolymerization initiator of triazine compounds such as -s-triazine.

In this invention, content of a photoinitiator is 10-120 mass parts normally with respect to 100 mass parts of (C) polyfunctional monomers, Preferably it is 10-100 mass parts, More preferably, it is 10-10 mass parts. 70 parts by mass.
If the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the colored layer tends to easily fall off 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 the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 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-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anti-aggregation agents such as sodium acrylate; Residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (me A) Development improver such as acrylate.

-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;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; 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, propylene glycol diacetate, 1,3-butylene glycol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate Formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- 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 the total concentration of each component excluding the solvent of the composition is 5 from the viewpoint of the coating property and storage stability of the resulting radiation-sensitive composition. An amount of ˜50 mass% and further 10˜40 mass% is desirable.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method, for example, by mixing the components (A) to (D) together with a solvent and other components optionally added. can do. As a preferable preparation method, for example, a bead mill, a roll mill, or the like is used together with a part of the component (B) in the presence of (A) a coloring agent in a solvent, a dispersing agent and, if necessary, a dispersing aid. Then, mix and disperse while pulverizing to obtain a pigment dispersion, which is prepared by adding (B) to (D) components and, if necessary, additional solvent and other components and mixing them. A method can be mentioned.

Next, a method for producing the color filter of the present invention using the colored radiation-sensitive composition of the present invention will be described.
The method for producing a color filter usually includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the coloring radiation sensitive composition of this invention on a board | substrate.
(2) A step of exposing a YAG third harmonic laser to 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) Process-
First, on the surface of the substrate, if necessary, a light shielding layer (black matrix) is formed so as to partition a portion for forming a pixel, and, for example, a red (A) colorant is contained on the substrate. The colored radiation-sensitive composition of the present invention 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 coloring 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-
Thereafter, a YAG third harmonic laser is exposed to at least a 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. Laser light is superior in directivity and convergence compared to lamp light, and it is easy to reduce the irradiation area. Therefore, if laser light is used, the pattern can be reduced even if the photomask is downsized or not used. Formation is possible.
A YAG laser is a laser with a wavelength of 1064 nm that oscillates when a rod doped with neodymium ions or the like in YAG (a garnet structure crystal made of a complex oxide of yttrium and aluminum) is excited by a laser diode or the like. The YAG third harmonic laser used in the present invention is a laser whose short length is shortened to one third by passing the YAG laser through a wavelength conversion element made of a nonlinear crystal, and its wavelength is 355 nm. is there. Ordinary radiation-sensitive compositions do not necessarily have sufficient sensitivity to the laser, and the linearity of the formed pattern edge tends to deteriorate. According to the radiation sensitive composition of the present invention, such a problem does not occur.
Exposure of YAG laser is usually 10~1,500J / m ^2, is divided into one or more times, the coating film as the accumulated exposure amount is 10~1,500J / m ² Irradiate.

-(3) Process-
Then, it develops using a developing solution, Preferably an alkaline 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 black radiation-sensitive composition containing a black colorant (A).

Color liquid crystal display element The color liquid crystal display element of the present invention comprises a color filter produced by the above-described method of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

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

(B) Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 0.5 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid and N-phenylmaleimide 20 Part by mass, 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, and 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMPII-20P manufactured by Sakai Chemical Industry Co., Ltd.) as a molecular weight regulator And replaced 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 5 hours for polymerization to obtain an alkali-soluble resin solution (solid content concentration = 33.3% by mass). The obtained resin was Mw = 25,000 and Mn = 12,000. This alkali-soluble resin is referred to as “resin (B-1)”.

Synthesis example 2
In a flask equipped with a condenser and a stirrer, 44 parts by mass of p-vinylbenzyl glycidyl ether, 40 parts by mass of N-phenylmaleimide, and 16 parts by mass of benzyl methacrylate are dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate. 4 parts by mass of 2′-azobisisobutyronitrile and 6 parts by mass of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the flask was heated to 80 ° C. with stirring and reacted for 5 hours to obtain a precursor resin solution.
200 parts by mass of the obtained precursor resin solution, 11 parts by mass of methacrylic acid, 0.2 parts by mass of p-methoxyphenol, 0.2 parts by mass of tetrabutylammonium bromide and 300 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask. The reaction was carried out at a temperature of 120 ° C. for 9 hours. As a result, 1 equivalent of methacrylic acid reacted with 1 equivalent of epoxy group of the precursor resin. Further, 16 parts by mass of succinic anhydride was added and reacted at 80 ° C. for 6 hours. The reaction mixture was washed twice with the liquid temperature maintained at 80 ° C. and concentrated under reduced pressure to obtain a resin solution containing 20% by mass of an alkali-soluble resin. The obtained resin was Mw = 8,000 and Mn = 3,100. This alkali-soluble resin is referred to as “resin (B-2)”.

Synthesis example 3
In a flask equipped with a condenser and a stirrer, 30 parts by mass of N-phenylmaleimide, 20 parts by mass of methacrylic acid, 20 parts by mass of styrene, 30 parts by mass of benzyl methacrylate, 200 parts by mass of cyclohexanone, 2,2′-azobisbutyronitrile 3.0 parts by mass and 2.0 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were mixed and reacted at 80 ° C. for 3 hours to obtain a precursor resin solution.
20 parts by mass of the obtained precursor resin (in terms of solid content), 0.2 parts by mass of p-methoxyphenol, 0.2 parts by mass of tetraethylammonium chloride, and 40 parts by mass of cyclohexanone were charged into a flask, and 3,4-epoxycyclohexylmethyl 2.1 parts by mass of acrylate was added and reacted at 90 ° C. for 30 hours. As a result, 1 equivalent of methacrylic acid in the precursor resin reacted with 1 equivalent of epoxy group of 3,4-epoxycyclohexylmethyl acrylate. The reaction mixture was washed twice with the liquid temperature maintained at 80 ° C. and concentrated under reduced pressure to obtain a resin solution containing 20% by mass of an alkali-soluble resin. The obtained resin was Mw = 16,200 and Mn = 6,500. This alkali-soluble resin is referred to as “resin (B-3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 13 parts by mass of methacrylic acid, 77 parts by mass of benzyl methacrylate, -10 parts by weight of hydroxyethyl methacrylate and 5 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent were charged, and after nitrogen substitution, the reaction solution was heated to 80 ° C while gently stirring. The polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobisisobutyronitrile was added, and polymerization was continued for 1 hour to obtain a precursor resin solution. .
After adding 10 parts by mass of 1,1- (bisacryloyloxymethyl) ethyl isocyanate and 0.1 part by mass of 4-methoxyphenol to the obtained precursor resin solution, 1 hour at 40 ° C. and 2 hours at 60 ° C. Reacted for hours. The progress of the reaction between the isocyanate group derived from 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the hydroxyl group in the precursor resin was confirmed by IR (infrared absorption) spectrum. It was confirmed that the peak near 2270 cm ⁻¹ derived from the isocyanate group of 1,1- (bisacryloyloxymethyl) ethyl isocyanate decreased with the progress of the reaction. In this way, an alkali-soluble resin having a solid concentration of 35% by mass was obtained. The obtained resin was Mw = 17,000 and Mn = 6,800. This alkali-soluble resin is referred to as “resin (B-4)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 800 parts by mass of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the flask, and at the same temperature, 60 parts by mass of styrene, 60 parts by mass of methacrylic acid, 65 of methyl methacrylate. A mixture of parts by mass, 65 parts by mass of butyl methacrylate and 10 parts by mass of azobisisobutyronitrile was added dropwise over 1 hour, and further reacted at 100 ° C. for 3 hours, and then 2 parts by mass of azobisisobutyronitrile was added. What was dissolved in 50 parts by mass of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an alkali-soluble resin solution. The obtained resin was Mw = 30,000 and Mn = 14,000. After cooling the obtained alkali-soluble resin solution to room temperature, about 2 g was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was further added so that the nonvolatile content became 20%. It was adjusted. Let the obtained alkali-soluble resin be "resin (B-5)."

Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment red 254 / C.I. I. Pigment red 177 / C.I. I. Pigment Yellow 150 = 40/55/5 (weight ratio) mixture 15 parts by weight, Dispersbyk-2001 / BYK-LPN21116 = 40/60 (mass ratio) mixture 4 parts by weight (solid content conversion), (B) alkali A pigment dispersion liquid (B-1) as a soluble resin was treated with a bead mill using 5 parts by mass (in terms of solid content) and propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 24% by mass. R) was prepared.

Preparation Example 2
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 70/30 (mass ratio) 15 parts by mass of the mixture, 4 parts by mass of BYK-LPN21324 as a dispersant (in terms of solid content), 5 parts by mass of resin (B-1) as (B) alkali-soluble resin ( A pigment dispersion (G) was prepared in the same manner as in Preparation Example 1 using a solid content conversion) and propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration was 24% by mass.

Preparation Example 3
(A) C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 90/10 (mass ratio) 12 parts by mass of the mixture, 4 parts by mass of Disperbyk-165 as a dispersant (in terms of solid content), (B) 5 parts by mass of resin (B-1) as an alkali-soluble resin ( A pigment dispersion (B) was prepared by treating in the same manner as in Example 1 using a solid content) and propylene glycol monomethyl ether acetate as a solvent so that the solid concentration was 21% by mass.

Example 1
Pigment dispersion (R) 100 parts by mass, (B) 4 parts by mass of resin (B-2) as an alkali-soluble resin (solid content conversion), (C) 8 parts by mass of dipentaerythritol hexaacrylate as a polyfunctional monomer (D) Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Special) as a photopolymerization initiator 1 part by mass, trade name Irgacure OX02), 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole manufactured by Tea Chemicals Co., Ltd. 0.5 Part by weight, 0.44 part by weight of 4,4′-bis (diethylamino) benzophenone, 0.2 part by weight of 2-mercaptobenzothiazole, and solid ethyl ethyl 3-ethoxypropionate as a solvent There were mixed so that the 25 wt%, the liquid composition (S-1) was prepared.

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

Formation and Evaluation of Pattern 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 2 minutes to obtain a film thickness of 2.5 μm. A coating film was formed. Subsequently, after cooling this board | substrate to room temperature, the YAG 3rd harmonic laser was irradiated to the coating film on a board | substrate through a photomask so that integrated exposure amount might be 200 and 400 J / m < ² >. Thereafter, shower development was performed by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds at a developing pressure of ² kgf / cm ² (nozzle diameter 1 mm) onto the coating film on the substrate. Next, post-baking was performed at 220 ° C. for 30 minutes to form a 90 μm stripe pixel pattern on the substrate.
Next, when the stripe pixel pattern formed on the substrate was observed with an optical microscope, no chipping was observed on the edge of the pixel pattern. Further, when the cross section of the pixel pattern on the substrate was observed with a scanning electron microscope (SEM), no undercut was observed and the linearity was good. Further, the remaining film ratio calculated by the following formula was 87.3% at an exposure amount of 200 J / m ² and 90.6% at an exposure amount of 400 J / m ² .
Residual film ratio = (film thickness after post-baking / film thickness after exposure) × 100
The linearity of the pixel pattern was evaluated using the following index.
○: Unevenness at the pattern edge portion is less than 1.5 μm Δ: Unevenness at the pattern edge portion is not less than 1.5 μm and less than 3 μm ×: Unevenness at the pattern edge portion is not less than 3 μm

Examples 2-8 and Comparative Examples 1-6
Liquid compositions (S-2) to (S-13) were prepared in the same manner as in Example 1 except that the types and amounts of the components 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-13) were used instead of the liquid composition (S-1). The results are shown in Table 2. In Comparative Example 6, the liquid composition (S-1) was used for exposure with a XeCl excimer laser.

In Table 1, each component is as follows.
C-1: Dipentaerythritol hexaacrylate C-2: Pentaerythritol tetraacrylate D-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 -(O-acetyloxime) (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals)
D-2: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole D-3: 4,4′-bis (diethylamino) benzophenone D-4: 2-mercaptobenzothiazole D-5: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (trade name IRGACURE OX01, Ciba Specialty・ Made by Chemicals
D-6: 2,4-diethylthioxanthone D-7: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, Ciba Specialty Chemicals) Made)
D-8: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)

In Examples 1-8, the integrated exposure amount 200 J / m ² and 400 J / m ² of the undercut also in any case, chipping does not occur, residual film ratio is high, were also linearity good.
On the other hand, in Comparative Examples 1 to 3, the linearity was not good, and particularly when the integrated exposure amount was 200 J / m ² , the pattern was chipped and the remaining film rate was low.
In Comparative Example 4, when the integrated exposure amount was 200 J / m ² , the pattern could not be formed, and when the integrated exposure amount was 400 J / m ² , the pattern was chipped, the remaining film rate was low, and the linearity was good. There wasn't.
In Comparative Example 5, the linearity was not good.
In Comparative Example 6, chipping occurred in the pattern. Therefore, it turns out that a liquid composition (S-1) is suitable for YAG 3rd harmonic laser exposure.

Claims (6)

A colored radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (B) the alkali-soluble resin is It contains a polymer having an acidic functional group and a polymerizable unsaturated group, and (D) the photopolymerization initiator is a thioxanthone compound and the following formula (1)

(In formula (1), R ¹ and R ² are, independently of each other, represents an alkyl group having 1 to 6 carbon atoms, R ³ is an optionally substituted alkyl group having 1 to 6 carbon atoms, C1-C20 alkoxy group or following formula (2)

(In the formula (2), R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, and “*” represents a bond.) . )
A colored radiation-sensitive composition for YAG third-harmonic laser exposure, comprising at least one selected from the group consisting of compounds represented by: and an O-acyloxime compound.   (D) The colored radiation-sensitive composition according to claim 1, wherein the photopolymerization initiator further contains a biimidazole compound.   The colored radiation-sensitive composition according to claim 1 or 2, wherein the O-acyloxime compound is a compound having a carbazole structure.   The color filter provided with the colored layer formed using the colored radiation-sensitive composition for YAG 3rd harmonic laser exposure in any one of Claims 1-3.   A color liquid crystal display device comprising the color filter according to claim 4.   (1) forming a coating film of the colored radiation-sensitive composition according to any one of claims 1 to 3 on a substrate; and (2) applying a YAG third harmonic laser to at least a part of the coating film. A method for producing a color filter including a step of exposing.