JP5510080B2 - Coloring composition for color filter, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a color liquid crystal display element. More specifically, the present invention is used for a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, and the like. The present invention relates to a coloring composition useful for forming a coloring pattern of a color filter, a color filter including a coloring pattern formed using the coloring composition, and a color liquid crystal display device including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored thermosetting resin composition (Patent Document 4) is also known.

  By the way, it is known that it is effective to use a dye as a colorant in order to realize high contrast of a liquid crystal display element and high definition of a solid-state imaging element (Patent Documents 5 to 7). And as disclosed in Patent Documents 5 to 7, in a colored composition containing a dye, a curing system in which a polyfunctional acrylate or alkoxymethylmelamine resin and a photopolymerization initiator are combined is mainly employed.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP-A-2005-99584 JP 2007-219466 A JP 2007-316179 A

  However, a color pattern formed using a conventional coloring composition containing a dye has a problem that the heat resistance and solvent resistance are significantly inferior to a coloring pattern formed using a pigment-dispersed coloring composition. was there. Therefore, there is a strong demand for the development of a coloring composition that can form a colored pattern with good heat resistance and solvent resistance even when a dye is used.

  Therefore, the subject of this invention is providing the coloring composition which can form a coloring pattern with favorable heat resistance and solvent resistance, even if it is a case where dye is used as a coloring agent. Furthermore, the subject of this invention is providing the color liquid crystal display element which comprises the color filter provided with the coloring pattern formed from the said coloring composition, and the said color filter.

  In view of such circumstances, the present inventors have conducted extensive research and found that the above-mentioned problems can be solved by using a crosslinking agent having both an epoxy cured site and a sol-gel cured site, and the present invention has been completed. It came to do.

  That is, the present invention relates to (A) a colorant, (B) a binder resin, and (C) a crosslinking agent having two or more epoxy groups and two or more alkoxy groups bonded to silicon atoms (hereinafter referred to as “( C) a specific crosslinking agent ").) And a coloring composition for a color filter.

The present invention also provides a color filter provided with a colored pattern formed using the colored composition, and a color liquid crystal display device comprising the color filter.
Furthermore, the present invention provides a method for producing a color filter comprising (1) a step of forming a colored pattern using the colored composition, and (2) a step of post-baking the colored pattern at 180 ° C. or lower. It is. Here, the “coloring pattern” means each color pixel, black matrix, black spacer, etc. used in the color filter.

If the coloring composition for color filters of this invention is used, even if it is a case where dye is used as a coloring agent, the color filter which has a coloring pattern with favorable heat resistance and solvent resistance can be obtained. Furthermore, if the coloring composition for color filters of this invention is used, it will become possible to manufacture a color filter by the post-baking temperature lower than before.
Therefore, the coloring composition for color filters of the present invention includes color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for the production of various color filters.

Hereinafter, the present invention will be described in detail.
Color Filter Color Composition Hereinafter, the components of the color filter color composition of the present invention (hereinafter simply referred to as “color composition”) will be described.

-(A) Colorant-
The (A) colorant in the present invention is not particularly limited as long as it has colorability, and colors and materials can be appropriately selected according to the use of the color filter. Specifically, any of pigments, dyes, and natural pigments can be used as the colorant. However, since color filters require high color purity, brightness, contrast, etc., pigments and / or dyes can be used. preferable.

  The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). . Specific examples include those with the following color index (CI) names.

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 180, 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 1, C.I. 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.

  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.

  In the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment is preferably used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  In addition, the dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like. For example, the following color index (CI) names are attached. Can be mentioned.

C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent yellow 179;
C. I. Solvent Red 45, C.I. I. Solvent red 49;
C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent orange 56;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent blue 67;

C. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 76;
C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid Red 151;
C. I. Acid Orange 51, C.I. I. Acid Orange 63;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90;
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 27.

  In this invention, a coloring agent can be used individually or in mixture of 2 or more types.

  By the way, in a coloring composition for a color filter, by using a dye as a colorant, it is possible to achieve high brightness and high contrast that cannot be achieved by a pigment alone. However, when a dye is used as the colorant, the heat resistance, solvent resistance, etc. of the pixel of the colored composition are significantly deteriorated. According to the coloring composition of the present invention, it is possible to obtain a coloring composition capable of forming a pixel having good heat resistance and solvent resistance even when a dye is used as a coloring agent.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. The “solid content” here is a component other than the solvent described later.

  In the present invention, when a pigment is used as a colorant, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant can be obtained commercially. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), As polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.), polyethylene As imine, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and as polyester, Ajisper PB821, Ajisper PB822, Ajisper PB880 ( Mention may be made of the Moto Fine-Techno Co., Ltd.), and the like.

These dispersants can be used alone or in admixture of two or more.
The content (solid content) of the dispersant is usually 100 parts by mass or less, preferably 1 to 70 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the pigment. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

  Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (n = 2 -10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Glyce Mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meta ) (Meth) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane 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 unsaturated monomers (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. Moreover, the ratio (Mw / Mn) of polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is preferable. Is 1.0 to 5.0, more preferably 1.0 to 3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, (B) binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of (B) binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) Specific cross-linking agent-
The coloring composition of the present invention contains a specific crosslinking agent, that is, a crosslinking agent having two or more epoxy groups and two or more alkoxy groups bonded to a silicon atom as a crosslinking agent. Thus, it becomes possible to form a strong coloring pattern by using a specific cross-linking agent having both an epoxy curing site and a so-called sol-gel curing site. In the present invention, the epoxy group means a group having a cyclic ether structure, and is preferably an oxiranyl group or an oxetanyl group.

  The specific crosslinking agent is not particularly limited as long as it has two or more epoxy groups and two or more alkoxy groups bonded to a silicon atom. For example, a compound having a hydroxyl group and two or more epoxy groups And an alkoxysilane or a partial condensate thereof, can be obtained by subjecting it to a transesterification reaction between the hydroxyl group and the alkoxy group.

  The compound having a hydroxyl group and two or more epoxy groups is not particularly limited as long as it has a hydroxyl group and two or more epoxy groups. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type In addition to bisphenol type epoxy resins such as epoxy resins and bisphenol type epoxy resins such as bisphenol S type epoxy resins, hydrogenated bisphenol A type epoxy resins and biphenyl type epoxy resins, polyhydric alcohol type epoxy resins can be mentioned.

  Bisphenol type epoxy resins can be obtained by reaction of bisphenols with haloepoxides such as epichlorohydrin or β-methylepichlorohydrin. Bisphenols include, for example, reaction products of phenol and aldehydes such as formaldehyde, acetaldehyde, and acetone, or ketones such as acetophenone, cyclohexanone, and benzophenone, oxidation of dihydroxyphenyl sulfide with peracid, and etherification of hydroquinones. What was obtained by reaction etc. is mentioned. The polyhydric alcohol type epoxy resin can be obtained by a reaction between a polyhydric alcohol and a haloepoxide.

  In the present invention, as the resin having a hydroxyl group and two or more epoxy groups, a copolymer containing an unsaturated monomer having an epoxy group and an unsaturated monomer having a hydroxyl group as structural units is used. May be. Examples of the unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. P-vinylbenzylglycidyl ether, 3- (vinyloxymethyl) -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, and the like. Can be mentioned. Examples of the unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2-10) Mono (meth) acrylate, p-hydroxystyrene, p-hydroxy-α-methylstyrene, 4-hydroxyphenyl (meth) acrylate, and the like.

  Further, the copolymer may contain a structural unit other than an unsaturated monomer having an epoxy group and an unsaturated monomer having a hydroxyl group. As a monomer that gives such a structural unit, for example, , The unsaturated monomer (b1) and the unsaturated monomer (b2).

  The copolymer can be produced by the same method as the binder resin (B), and the structure of the copolymer is not particularly limited. A random copolymer, an alternating copolymer, and a block copolymer are used. Any of these may be used. The copolymerization ratios of the unsaturated monomer having an epoxy group, the unsaturated monomer having a hydroxyl group, and the monomer other than these in the copolymer are such that a desired (C) specific crosslinking agent is obtained. It can be set as appropriate.

  Among these, as the resin having a hydroxyl group and two or more epoxy groups, a bisphenol type epoxy resin is preferable, and a bisphenol A type epoxy resin is particularly preferable.

  On the other hand, as alkoxysilane, the compound represented by following formula (1) is mentioned, for example, As for the partial condensate, the number of siloxy units becomes like this. Preferably it is 2-10, More preferably, it is 2-8.

(In the formula (1), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and R ² independently represents the number of carbon atoms. 1-4 represents an alkyl group, and n is 0 or 1.)

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group and a naphthyl group. Among these, as R ¹ , a methyl group is preferable.

The alkyl group having 1 to 4 carbon atoms for R ^2, a methyl group is preferable.

Examples of the substituent in R ¹ include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, and an alkoxy group.

  Specific examples of the compound represented by the general formula (1) include tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and isopropyltrimethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, dimethyldimethoxy Examples thereof include silane and diethyldimethoxysilane. Among these, tetramethoxysilane, methyltrimethoxysilane and the like are preferable.

  Alkoxysilane partial condensates can also be obtained commercially. For example, methyl silicate 51 is used as the tetramethoxysilane partial condensate, and silicate 40 and 45 (above, Tama Chemical Industries, Ltd.) as the tetraethoxysilane partial condensate. Manufactured) and the like.

For the transesterification reaction between a resin having an epoxy group and a hydroxyl group and alkoxysilane or a partial condensate thereof, for example, a method described in JP-A-2001-59011 can be employed. Moreover, the compounding ratio of the resin having an epoxy group and a hydroxyl group and the alkoxysilane or a partial condensate thereof is the silica (SiO ₂ ) equivalent mass / epoxy of the alkoxysilane or the partial condensate from the viewpoint of curability of the colored pattern. The ratio with respect to the mass of the resin having a group and a hydroxyl group is preferably 0.01 to 1.2, particularly preferably 0.1 to 0.8.

  (C) The specific crosslinking agent preferably has an epoxy equivalent of 100 to 5,000 g / eq, more preferably 200 to 2,000 g / eq. Here, “epoxy equivalent” is a value measured by potentiometric titration in accordance with JIS K 7236.

  (C) The specific cross-linking agent can also be obtained commercially. For example, as silane-modified bisphenol type epoxy resin, Composelan E102, E102B, E103, E103B, E201, E202C (Arakawa Chemical Industries Ltd.) Company-made).

  In the present invention, the content of the (C) specific crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 10 to 500 parts by mass with respect to 100 parts by mass of the (B) binder resin. In this case, when there is too little content of a specific crosslinking agent, there exists a possibility that a desired effect may not be acquired. On the other hand, when there is too much content of a specific crosslinking agent, there exists a possibility that a coloring pattern may be easily missing at the time of alkali image development.

In this invention, sclerosis | hardenability can be improved further by using other crosslinking agents other than a specific crosslinking agent with a specific crosslinking agent as a crosslinking agent.
Examples of the other cross-linking agent include compounds having two or more ethylenically unsaturated groups, compounds having two or more N-alkoxymethylamino groups, and the like. In the present invention, the other crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the “compound having two or more (meth) acryloyl groups” include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, and caprolactone-modified polyfunctional compounds. Functional (meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxyl group with polyfunctional isocyanate, (meth) acrylate having hydroxyl group And a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting an acid anhydride with the acid anhydride.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and triglyceride. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds such as pentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Examples of the “compound having two or more N-alkoxymethylamino groups” include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure are chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are a concept including a melamine compound, a benzoguanamine compound or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl). ) Benzoguanamine, N, N, N, N-tetra (alkoxymethyl) glycoluril and the like.

Among these other cross-linking agents, polyfunctional (meth) acrylates obtained by reacting tri- or higher valent aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyhydric compounds, in order to enhance the desired effect. Functional (meth) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl) benzoguanamine is preferred. Among polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate are particularly preferred, and among polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, A compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride is particularly preferred.
In this invention, another crosslinking agent can be used individually or in mixture of 2 or more types.

  The content of the other cross-linking agent in the present invention is preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (B) binder resin.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain (D) a photopolymerization initiator. The (D) photopolymerization initiator used in the present invention is the above-mentioned (C) specific cross-linking agent and / or other ones used as required by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active species capable of initiating polymerization of a crosslinking agent. Thereby, radiation sensitivity can be provided to a coloring composition.

  Examples of such a photopolymerization initiator include a photo radical generator, a photo acid generator, and a photo base generator. In the present invention, it is preferable to use a photo radical generator in combination with a photo acid generator or a photo base generator as a photopolymerization initiator. By using a photoacid generator or a photobase generator, the sol-gel curing reaction of the (C) specific crosslinking agent can be utilized, and the curability of the colored pattern can be further enhanced.

As a preferable compound among the photo radical generators,
Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. A thioxanthone compound of
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;
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1, Biimidazole compounds such as 2'-biimidazole;

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 (triazine-based compounds such as trichloromethyl) -s-triazine;
1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 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) and the like O-acyloxime compounds.

  In the present invention, the photoradical generator can be used alone or in admixture of two or more.

Examples of the photoacid generator include benzoin tosylate, pyrogallol tritosylate, pyrogallol trimesylate, 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, diphenyldisulfone, di (p-tolyl) disulfone, In addition to phthalimidyl triflate, 1,8-naphthalimidyl triflate, tri (nitrobenzyl) phosphate, trianisofate phosphate, known diaryl iodonium salts, triaryl sulfonium salts and the like can be mentioned. The triazine compounds listed in the above photo radical generator are components that also function as a photo acid generator.
In this invention, a photo-acid generator can be used individually or in mixture of 2 or more types.

Examples of the photobase generator include orthonitrobenzyl carbamates such as bis [[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine and [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] α, α-dimethyl-3,5-dimethoxybenzylcarbamate such as hexamethylenediamine can be exemplified.
In this invention, a photobase generator can be used individually or in mixture of 2 or more types.

In the present invention, when a photo radical generator is used, the content thereof is preferably 0.01 to 120 parts by mass, particularly 1 to 100 parts by mass of the compound having two or more (meth) acryloyl groups. -100 mass parts is preferable.
Moreover, when using a photo-acid generator or a photobase generator, 0.1-100 mass parts is preferable with respect to 100 mass parts of said (C) specific crosslinking agents, Especially 1-50 masses. Part is preferred.
By using a photopolymerization initiator in such a manner, a colored composition capable of forming a colored pattern with good heat resistance and solvent resistance can be obtained.

  In addition, in this invention, when using a photoinitiator, a sensitizer can also be used together. 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, Anthracene, 2-tert-butylanthracene, perylene and the like can be mentioned.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include a thermal acid generator such as a sulfonium salt (excluding the triarylsulfonium salt), a benzothiazonium salt, an ammonium salt, a phosphonium salt, and a sulfonimide compound.

-Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
As said solvent, (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has appropriate volatility. You can choose to use.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, 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, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl 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, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl 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, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents may be used alone or in combination of two or more.

  Although content of a solvent is not specifically limited, From viewpoints of the applicability | paintability of a coloring composition obtained, stability, etc., the total density | concentration of each component except the solvent of the said coloring composition is 5-50. An amount of mass% is preferred, and an amount of 10 to 40 mass% is particularly preferred.

Color filter and method for producing the same The color filter of the present invention comprises a colored pattern formed from the colored composition of the present invention. The method for producing a color filter usually includes at least the following steps (1) to (2).
(1) A step of forming a colored pattern on the substrate using the colored composition of the present invention.
(2) Step of post-baking the colored pattern

  Hereinafter, these steps will be sequentially described.

-(1) Step of forming a colored pattern on the substrate using the colored composition of the present invention-
As a method for forming a colored pattern on a substrate, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying the coloring composition of the present invention containing a red colorant on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, after exposing the coating film through a photomask and developing with an alkali developer, the unexposed portions of the coating film were dissolved and removed, whereby red pixel patterns were arranged in a predetermined arrangement. A pixel array is formed.

  Next, using each colored composition of green or blue, and applying each colored composition, pre-baking, exposing, developing and post-baking in the same manner as described above, the green pixel array and the blue pixel array are formed on the same substrate. Sequentially formed on top. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  In addition, the black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method, but the present invention contains a black colorant. It is also possible to form in the same manner as in the case of forming the pixel using the colored composition.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
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 coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. can be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm, as the film thickness after drying.

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-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. In addition, it is usually washed with water after alkali development.
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 5 to 300 seconds at room temperature.

  Further, as a second method for forming a colored pattern on a substrate, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723, JP-A-2000-310706, etc. is adopted. be able to. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the colored composition of the present invention containing, for example, a red colorant is discharged into the formed partition wall by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary to form a red pixel pattern.

  Subsequently, using each coloring composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used for forming the color filter, the light source of radiation, and the prebaking method and conditions are the same as those in the first method described above.

-(2) Step of post-baking the colored pattern-
After the colored pattern is formed, the colored pattern is cured by performing post-baking. The post-baking conditions are usually 120 to 280 ° C. and about 10 to 60 minutes. The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.
If the colored composition of the present invention is used, a good colored pattern such as solvent resistance can be obtained even if the post-baking temperature is lower than that of the conventional one. More specifically, even when the post-bake temperature is 200 ° C. or lower, or even 180 ° C. or lower, a colored pattern having sufficient solvent resistance can be obtained.

  In addition, after forming a protective film on the pixel pattern obtained through the steps (1) and (2) as necessary, a transparent conductive film is formed by sputtering, and a spacer is further formed to form a color filter. It can also be. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter 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 faces each other via the 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 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 of pigment dispersion Preparation Example 1
As a coloring agent, C.I. I. Pigment green 58 / C.I. I. Solvent yellow 82 = 15 parts by mass of 60/40 (mass ratio) mixture, BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant, 10 parts by mass (nonvolatile component = 40% by mass), and propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (a-1, solid content concentration = 19% by mass).

Preparation Example 2
As a coloring agent, C.I. I. Pigment green 58 / C.I. I. Pigment Yellow 150 = 80/20 (mass ratio) 15 parts by mass of a mixture, BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant, 10 parts by mass (non-volatile component = 40% by mass), and propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (a-2, solid content concentration = 19% by mass).

(B) Synthesis of binder resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2 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 and 20 parts by weight of N-phenylmaleimide. , 55 parts by weight of benzyl methacrylate, 10 parts by weight of styrene and 3 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (manufactured by NOF Corporation, NOFMER MSD) as a molecular weight regulator, 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 a binder resin solution (solid content concentration = 33% by mass). The obtained resin was Mw = 16,000 and Mn = 7,000. This binder resin is referred to as “binder resin (b-1)”.

(C) Synthesis of specific crosslinking agent Synthesis Example 2
(C) a specific crosslinking agent solution (solid content concentration = 50) obtained by partially condensing a bisphenol A type epoxy resin and a tetramethoxysilane partial condensate according to the description in Example 2 of JP-A-2001-59011 Mass%). Let this specific crosslinking agent be a specific crosslinking agent (c-1). The specific crosslinking agent (c-1) was epoxy equivalent = 869 g / eq.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 16 parts by mass of 2,2′-azobisisobutyronitrile and 400 parts by mass of propylene glycol monomethyl ether acetate, followed by 30 parts by mass of methacrylic acid and 40 parts by mass of N-phenylmaleimide. , 90 parts by mass of benzyl methacrylate, 40 parts by mass of p-hydroxy-α-methylstyrene and 2,4-diphenyl-4-methyl-1-pentene (manufactured by NOF Corporation, trade name: NOFMER MSD) as a molecular weight regulator 8 parts by mass were charged 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 a resin solution (solid content concentration = 32% by mass).
Next, 430 parts by mass of the obtained resin solution and 100 parts by mass of dimethylformamide were added to a reactor equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, and the mixture was heated to 100 ° C. and stirred. Furthermore, 47.6 parts by mass of a tetramethoxysilane partial condensate (trade name: methyl silicate 51, manufactured by Tama Chemical Co., Ltd.) and 1 part by mass of dibutyritin dilaurate as a catalyst were charged, and a methanol removal reaction was performed at 110 ° C. for 6 hours. . After cooling to 80 ° C. and distilling off methanol and dimethylformamide under reduced pressure, the mixture was diluted with propylene glycol monomethyl ether acetate to obtain a (C) specific crosslinking agent solution having a solid concentration of 50%. Let this specific crosslinking agent be a specific crosslinking agent (c-2). The specific crosslinking agent (c-2) was epoxy equivalent = 1980 g / eq.

Example 1
Preparation of coloring composition (A) C.I. I. 30 parts by weight of Solvent Blue 62, C.I. I. 20 parts by weight of Solvent Yellow 82, (B) 100 parts by weight of the binder resin (b-1) solution as the binder resin, (C) 100 parts by weight of the specific crosslinking agent (c-1) solution as the specific crosslinking agent, 50 parts by weight of biscort # 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a crosslinking agent, (D) ethanone as a photopolymerization initiator, 1- [9-ethyl- 20 parts by mass of 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (photo radical generator), iodonium, (4-methylphenyl) [4- 10 parts by weight of (2-methylpropylphenyl)]-hexafluorophosphate (photoacid generator) and a solvent as a solvent By mixing propylene glycol monomethyl ether acetate, solid concentration of 20 wt% coloring composition (S-1) was prepared.

Formation of colored pattern The colored composition (S-1) is applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form five coating films having a film thickness of 2.5 μm after pre-baking.
Next, after cooling these substrates to room temperature, the exposure dose of 300, 1,000 J / m ² was applied to the coating film through a photomask using a high-pressure mercury lamp, with radiation containing 365 nm, 405 nm, and 436 nm wavelengths. And exposed. Thereafter, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) on these substrates, Post baking was performed at 180 ° C. for 30 minutes to form a 200 × 200 μm dot pattern on the substrate.

Evaluation of development resistance In the above "colored pattern formation", when the film thickness ratio before and after the development of the dot pattern (film thickness after development x 100 / film thickness before development) is 95% or more, "A" The case where the film thickness ratio before and after the development was less than 95% or the chip pattern was found to be partially missing was evaluated as “B”, and the case where the pattern was completely peeled off from the substrate was evaluated as “C”. The evaluation results are shown in Table 2.

Evaluation of solvent resistance In the above “colored pattern formation”, a substrate on which a dot pattern was formed with an exposure amount of 1,000 J / m ² was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. As a result, when the dot pattern was retained after the immersion and the N-methylpyrrolidone after the immersion was not colored at all, “A”, the dot pattern was retained after the immersion, but the N-methylpyrrolidone after the immersion was The case where it was slightly colored was evaluated as “B”, the dot pattern peeled off from the substrate after immersion was observed, and the case where N-methylpyrrolidone after immersion was colored was evaluated as “C”. The evaluation results are shown in Table 2.

Evaluation of heat resistance In the above “colored pattern formation”, the substrate on which the dot pattern was formed with an exposure amount of 1,000 J / m ² was further heated at 180 ° C. for 30 minutes. The color change ΔEab ^* before and after additional heating was determined. The case where ΔEab ^* was less than 3 was evaluated as “A”, the case where it was 3 or more and less than 5 was evaluated as “B”, and the case where it was 5 or more was evaluated as “C”. The evaluation results are shown in Table 2.

Examples 2-7 and Comparative Examples 1-3
In Example 1, the colored composition was the same as Example 1 except that the types and amounts of (A) colorant, (C) crosslinking agent, and (D) photopolymerization initiator were changed as shown in Table 1. Was prepared. And about Examples 2-6 and Comparative Examples 1-2, it evaluated similarly to Example 1. FIG. Moreover, about Example 7 and Comparative Example 3, evaluation shown below was performed. The evaluation results are shown in Table 2.

Example 7 and Comparative Example 3
<Colored pattern formation by inkjet method>
Using an inkjet device Nanoprinter-1500S (manufactured by Microjet Co., Ltd.), the film thickness near the center of the pixel after drying is 2 in a pixel partitioned by a partition wall having a height of 2.0 μm, a length of 500 μm and a width of 150 μm. The colored composition (S-7) or the colored composition (S-10) was discharged so as to have a thickness of 0.0 μm. Next, after vacuum drying at 0.2 Torr, pre-baking on a hot plate at 90 ° C. for 5 minutes and further post-baking in a clean oven at 180 ° C. for 30 minutes to obtain a colored composition Cured.

<Evaluation of solvent resistance>
The substrate obtained in <Formation of colored pattern by inkjet method> was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. Then, the color change ΔEab ^* before and after immersion was determined. The case where ΔEab ^* was less than 3 was evaluated as “A”, the case where it was 3 or more and less than 5 was evaluated as “B”, and the case where it was 5 or more was evaluated as “C”.

<Evaluation of heat resistance>
The substrate obtained in <Formation of colored pattern by inkjet method> was further heated at 230 ° C. for 30 minutes. The color change ΔEab ^* before and after additional heating was determined. The case where ΔEab ^* was less than 3 was evaluated as “A”, the case where it was 3 or more and less than 5 was evaluated as “B”, and the case where it was 5 or more was evaluated as “C”.

In Table 1, each component is as follows.
a-3: C.I. I. Solvent Blue 62 (dye)
a-4: C.I. I. Solvent Yellow 82 (dye)
c-3: Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate (trade name Biscote # 802, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
d-1: iodonium (4-methylphenyl (4- (2-methylpropylphenyl))-hexafluorophosphate (photoacid generator, manufactured by Ciba Specialty Chemicals)
d-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (photo radical generator, trade name IRGACURE OX02 Manufactured by Ciba Specialty Chemicals)
d-3: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (photo radical generator, trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals)
d-4: 4,4′-bis (diethylamino) benzophenone (sensitizer)

Claims (8)

(A) a colorant, (B) a binder resin, and (C) a crosslinking agent that is a transesterification product of a resin having a hydroxyl group and two or more epoxy groups and an alkoxysilane or a partial condensate thereof. A coloring composition for a color filter. The coloring composition for color filters according to claim 1 , wherein the alkoxysilane is a compound represented by the following formula (1).

(In the formula (1), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and R ² independently of each other has 1 carbon atom. Represents an alkyl group of ˜4, and n is 0 or 1.) The hydroxyl group and a resin having two or more epoxy groups is a bisphenol epoxy resin, a color filter coloring composition according to claim 1 or 2. Furthermore, (D) The coloring composition of any one of Claims 1-3 containing a photoinitiator. (A) a colorant, (B) a binder resin, (C-1) a crosslinking agent having two or more epoxy groups and two or more alkoxy groups bonded to a silicon atom, (C-2) two or more A compound having an ethylenically unsaturated group, and (D) at least one photopolymerization initiator selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and an O-acyloxime compound; A colored composition for a color filter.   The color filter provided with the coloring pattern formed using the coloring composition for color filters of any one of Claims 1-5.   A color liquid crystal display device comprising the color filter according to claim 6. Forming a colored pattern using the colored composition according to any one of claims 1 to 5;
The manufacturing method of the color filter including the process of post-baking the said coloring pattern at 180 degrees C or less.