TW201205194A - Colored photocurable composition for color filter, color filter, method for producing color filter, and liquid crystal display device - Google Patents

Abstract

The present invention is to provide a colored photocurable composition for color filter with excellent pattern development capability, few residues on the substrate, a contact hole having a large aperture diameter after baking the pattern, and a high residual rate, and also provides a method for producing color filter with excellent color repeatability, a color filter, and a liquid crystal display device. There is provided a colored photocurable composition for color filter, which includes organic solvent (A), pigment (B), photopolymer initiator (C), polymerized chemical compound (D), and bonding agent (E). The polymerized chemical compound (D) includes chemical compound selected from at least one of (I) and (II), wherein (I) denotes polymerized chemical compound having 2 to 6 methyl-acryl groups, 1 to 6 hydroxyl groups from glycidyl group, and a ring structure except the aromatic ring; (II): polymerized chemical compound having 3 to 12 methyl-acryl groups, 1 to 12 hydroxyl groups from glycidyl group, and a side chain structure.

Description

201205194 VI. Description of the Invention: The present invention relates to a color filter using a photo-curable coloring group for a color filter, and a color filter for manufacturing the color filter. The liquid crystal display is worn; [Prior Art] A color filter is an indispensable component of a liquid crystal display. In terms of a small display device, a liquid crystal display is smaller than a CRT and is also equivalent in performance to crt in terms of performance, so a television screen, The computer screen and other display devices convert the CRT into a liquid crystal display. In recent years, the development of liquid crystal displays has also ranged from a screen area to a brain, a monitor, to a large screen, and requires high-quality electricity. Therefore, the color filter used therein has also been studied for increasing the substrate size for the purpose of improving the performance. Moreover, the color pattern is also exposed with a large area mask. This mask is very expensive to manufacture. How to reduce the cost of the mask becomes important. Thus, there is disclosed a method of forming a color light-passing sheet by using laser light (for example, refer to Patent Document 1) using a semiconductor laser. In this method, the laser output is small, and the exposure needs to be improved to improve productivity. Further, there has been proposed a method of manufacturing a color filter which does not use a large hood during exposure when the color filter is manufactured (see, for example, Patent Documents 2 and 3). However, when a high-output laser exposure is combined for productivity, the object, the component, and the actuator are produced on the element. In order to save electricity, it is gradually produced by small TVs. Patterning ° However, the time-consuming total price of the photo film to obtain the high-quality pattern -3 - 201205194 lack of pa or peeling, distortion, and requires both the production of improved and the shape of a good quality of the formation of. In the liquid crystal display device of the 'color-filter 〇n Array (the color filter is described below as COA on the array substrate), it is based on a Thin Film Transistor (hereinafter referred to as TFT). A color filter layer that also functions as an interlayer insulating film is formed. Therefore, in addition to the above-mentioned general requirements, the required characteristics of the color filter layer are required to have contact hole formation property, low permittivity, and gripper resistance as the required characteristics of the interlayer insulating film. As the required characteristics, a resin film is also provided as a protective layer on the color filter layer. In addition, the ugly blue line area is used to illuminate the color of the light-receiving layer. If x or straight pixels are used to cut the ultraviolet light, the pattern heat is 10,000 Å, and the enamel pigment is a blue pigment due to heat resistance. However, Ou Qing's absorbance is high and it is not easy to cause the problem that the halogen cannot be deteriorated when the ultraviolet light is patterned. In particular, in the contact area of the IT0 electrode and the coloring layer of the C〇a side, a circular or elliptical surface having a side length of 1 to 4 〇μηιΦ having a side length of 1 to 4 〇μηιΦ is required to have a high absorbance in a contact area of a rectangle to a cone. In the case of the post-baking, the post-baking is performed at a high temperature, and the formed contact hole is produced, and the light blueness such as light resistance is penetrated, and the photo-curing is hardened. In the formula, the driving substrates 1 to 40 are used. ι η 、 、 、 或是 或是 或是 或是 或是 或是 或是 或是 或是 或是 π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π When the problem of cracking of the picture of the hardening case is carried out, it is also proposed to use the triazabenzene skeleton in the etched field of the negative photosensitive composition in the case of manufacturing the color light-emitting sheet of the c〇A mode. The compound (for example, refer to Patent Document 4), 帷ά & fw is 驮4, but the pattern forming property black-4 - 201205194 has a fragrance as the reference is not sufficient. As the polymerizable compound, a ring-shaped epoxy acrylate has been proposed for use in a curable coloring composition (Recommendations 5 to 7), but the pattern formability is insufficient. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1 Japanese Patent Document 2 曰本特专利文件 3 曰本特特专利文件 4 Japanese Patent Document 5 Japanese Patent Document 6 曰本专专利文档 7 曰本专[ -1 No. 14602, the opening of the Japanese Patent Publication No. 2008-76709, No. 2008-5, No. 866, No. 2006-28455, No. 1, 1-1, 33, 599, No. 2, 894, 155, the specification of the No. 3901 807 [invented by the invention] [Problem] It is an object of the present invention to provide a color filter for a hole having a high pattern and a pattern of a residue on an unexposed portion after development, which has a high contact rate after being baked, and which has a large opening diameter. The photocurable coloring composition is a display device which is a method for producing a coloring and polishing method using the photocurable coloring composition. The color tone is good, the color filter is developed, the hole is formed, and the color reproduction is provided, and the liquid crystal L is used to solve the problem. The method for solving the above problem is the following one color filter light. (A) an organic solvent, (B) a pigment, (c, a tablet, a (D)-5-201205194 polymerizable compound, and (E) an adhesive, wherein the (D) polymerizable compound is selected One or more compounds of the following (I) and (II), (I): having two or more (6) or less (meth) acrylonitrile groups, and one or more and six or less hydroxyl groups derived from glycidyl groups And a polymerizable compound having a ring structure other than the aromatic ring; (II): having 3 or more and 12 or less (fluorenyl) acrylonitrile groups, one or more and 12 or less hydroxyl groups and branches derived from glycidyl groups <2> The photocurable coloring composition for a color filter according to <1>, wherein the ring structure other than the aromatic ring in the above (I) is selected from the group consisting of hexahydrophthalic acid a citric acid skeleton, a tetrahydrophthalic acid skeleton, a hydrogenated bisphenol A skeleton, One of a group of a cyclohexanedimethanol skeleton, an iso-cyanuric acid ring, and a tricyclodecane decyl alcohol skeleton. <3> A photocurable coloring composition for a color filter according to &lt;1&gt; The branched structure in the above (II) is one selected from the group consisting of a trihydrocarbyl propane skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, a sorbitol skeleton, and a glycerin skeleton. The light-curable coloring composition for a color filter according to any one of the above-mentioned items, wherein the (D) polymerizable compound further contains (111) having three or more and one or two The following (meth) acrylonitrile group, the number of the (mercapto) fluorenyl group divided by the molecular weight of the polymerizable compound is from 0.0067 to 0.01 14 or less, and the structure and the above (I), ( The photocurable coloring composition for a color filter according to any one of <1> to <4>, wherein the color filter is used for the light filter. Hardenability-6- 201205194 When the composition is colored to form a colored layer having a film thickness of 2 μm after drying The coloring layer is a photocurable coloring composition for a color filter of any one of the above items, wherein the coloring layer has a transmittance of 2% or less at a wavelength of 355 nm. The color-curable coloring composition for a color filter of any one of <1> to &lt;5&gt; The above-mentioned (B) pigment is a c-pigment blue 15:6. A method of producing a color filter comprising: the colored layer forming step' is a color according to any one of &lt;1 &gt; to &lt;6&gt; The filter is provided on the substrate with a photocurable coloring composition to form a coloring layer containing the colored composition; the exposing step 'exposing the colored layer into a pattern; and the developing step' is to expose the colored layer Developed to form a colored pattern. &lt;8&gt; The method of producing a color filter according to <7>, wherein the exposure step is an exposure step of exposing to a pattern using a laser of 355 nm. &lt;9&gt; The method for producing a color filter according to &lt;7&gt; or &lt;8&gt;, which is a color; the color filter is placed on a color filter of an array substrate (C〇i〇r_fiiter On Array) Production method. &lt;1〇&gt; A color filter manufactured by the method of producing a color filter according to any one of &lt;7&gt; to &lt;9&gt;. &lt;1 1&gt; A liquid crystal display device comprising a color filter such as &lt;1〇&gt;. [Effects of the Invention] According to the present invention, it is possible to provide a pattern having excellent developability and a small amount of residue on the substrate after undeveloped portions after development, and the opening diameter of the contact hole after the post-baking of the formed pattern is still A color filter having a large residual ratio of contact holes and a photocurable coloring composition for color filters, and a method for producing a color filter excellent in hue and excellent color reproducibility using the photocurable coloring composition , color filters, and liquid crystal display devices. 201205194 [Embodiment] Hereinafter, the present invention will be described in detail. The color filter of the color filter of the present invention contains (A) an organic solvent, (B) a pigment, (C) a photopolymerizable (D) polymerizable compound, and (e) an adhesive, wherein the prodrug compound is selected from the group consisting of (1) (hereinafter referred to as "specifically polymerizable compound" as appropriate) (1): one or more of two or more (mercapto) groups derived from glycidyl groups A polymerizable compound having a hydroxyl group or an outer ring structure; (a) a polymerizable compound having three or more and 12 or less (fluorenyl) one or more hydroxyl groups derived from a glycidyl group. The photocurable coloring composition of the present invention is used for the formation of a color pattern. The photocurable coloring matter of the present invention will be described in detail below. Further, in the present specification, an acrylonitrile group and a methyl group are referred to as a (fluorenyl) acrylonitrile group. &lt; (D) Polymerizable Compound&gt; The photocurable coloring composition of the present invention contains (D) a poly(1) of one or more compounds of the packages (1) and (II): two or more and six The following (meth) is a polymerizable compound having one or more of six or less hydroxyl groups and a ring structure having a ring structure (hereinafter referred to as a compound (I) as appropriate); the product is characterized by a combination initiator, The above-mentioned 'synthesis compound' acrylonitrile is described in (D) the above-mentioned compound y propylene group and the aromatic ring propylene group and the branched structure filter. "Polymerization--8-201205194 (II): One or more polymerizable compounds having three or more and 12 or less g derived from glycidyl groups (hereinafter referred to as "driving 5" The compound (I) is a compound having one or more and at least six or less ring structures other than an aromatic ring derived from a glycidyl group, as long as it is one of a propylene group or a methacryl group in the molecule. 'As a ring ring other than the aromatic ring, a cyclobutane ring skeleton, a cyclopentane ring skeleton alkane ring skeleton a heterocyclic skeleton such as a cyclobutene, a cyclopentene, a cyclohexanyl ring skeleton, a tetrahydrofuran ring skeleton, an anthracene skeleton, a pyrrole ring skeleton, a piperidine ring skeleton, a dicyanocyanate ring skeleton, or a tricyclononane ring. a bridging ring skeleton such as a skeleton, a spirulina, etc., wherein the color is not colored when heated, preferably a hexahydrophthalic acid skeleton, a tetrahydrobisphenol A skeleton, or a cyclohexane dimethanol skeleton. The sputum of methanol sputum is more preferably a tetrahydro-o-line A. The following shows that the preferred ring structure of i* represents a self-glycidyl-containing planer containing a (meth)(tetra)indenyl group from a spoon (曱(A) an acrylonitrile group, a hydroxyl group of 7 and a branched structure-complex compound (II)"). The cyclodene ring skeleton such as a cyclohexane ring skeleton or a cyclohexane ring skeleton may be exemplified by a compound having two or more or less or two or more and having a hydroxyl group in the molecule, and further having any structure. ° Each ring skeleton. a spirocyclic skeleton I1 such as a pyrrolizane triazide ring skeleton, an isodecane ring skeleton, a bicyclo ten t ring skeleton, and the like, and a hydrogen phthalic acid skeleton, an iso-cyanuric acid ring, Tricarboxylic acid skeleton, hydrogenation double ί* frame. The following structural formulas make t units and included parts. -9- 201205194

0

Ο hexahydrophthalic acid skeleton tetrahydro-o-p-dicarboxylic acid skeleton 1,1 —〇&quot;

Hydrogenated bisphenol fluorene skeleton cyclohexane decyl alcohol skeleton

Iso-cyanuric acid skeleton Tricyclic terpine-based diterpene alcohol skeleton The hydroxyl group derived from glycidyl group in a specific polymerizable compound will be described. If a compound having a cyclic structure and having an oxy group or a hydroxyl group, and a compound having a bond and having an oxy group or a trans group are added, for example, glycidyl (meth) acrylate, (meth) propylene oxime can be obtained. The adduct of the group, while the glycidyl group is opened to form a hydroxyl group. The carboxyl group thus obtained is derived from a glycidyl group which usually forms a secondary hydroxyl group. The hydroxyl group derived from the glycidyl group in the present invention means a hydroxyl group formed by a reaction of a compound having a glycidyl group. 201205194 言海~~ Λ % The base is light-curable in the alkaline development, and it does not show strong solubility as a carboxylic acid group.

It can be passed on to it.

The qualitative development was carried out moderately, and it was considered that the use of such a polymer compound ΰΤ H τ exhibited the effects of the present invention. The polymerizable compound (1) is one or both of two to four propylene groups or a field τ 1 acryl fluorenyl group in the molecule, and two molecules in the molecule are derived from 纟5^. a hydroxyl group-containing hydroxyl group, and further having a hexahydrophthalic or a hydrogenated bisphenol A skeleton as a ring structure other than the aromatic ring. The %·polymerizable compound (I) preferably has such a structure: The ring structure outside the aromatic ring has a central structure, and has two or more acrylonitrile-based fluorenyl fluorenyl groups at the terminal, and more than one or more glycidyl groups from the side chain. / Specific examples of the soil polymerizable compound (I) The following compounds can be exemplified. The synthetic olefins ~ 4 acid complexes or 201205194

OH

OH

OH 201205194

Corpse

〇 〇 〇

The polymerizable compound (II) is one or both of three or more and 12 or less acryloyl fluorenyl groups or fluorenyl fluorenyl groups in the molecule, and has one or more and 12 or less or less glycidyl groups in the molecule. A compound having a hydroxyl group and further having a branched structure may be a compound of any structure. Here, the branched structure refers to a tertiary or quaternary carbon source 13-201205194 in which a molecule other than hydrogen such as a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom is substituted in the molecule, and is centered on the branched structure. The structure has a structure in which three or more acryl fluorenyl groups or methacryl fluorenyl groups are present at the terminal. Specifically, it is a trihydrocarbyl propane skeleton, a neopentyl alcohol skeleton, a dipentaerythritol skeleton, a sorbitol skeleton, a glycerin skeleton, etc., and is preferably a trishydroxyhydrazine from the viewpoint of polymerizability, viscosity, and synthesis. The propane skeleton, the neopentyl alcohol skeleton, the dipentaerythritol skeleton, the sorbitol skeleton or the glycerin skeleton are particularly preferably a pentaerythritol skeleton, a dipentaerythritol skeleton, or a sorbitol skeleton. These preferred branched structures are shown below. In the following structural formula, * represents a structural unit containing a (fluorenyl) acrylonitrile group and a bonding site with a structural unit containing a hydroxyl group derived from a glycidyl group. -14- *-°x201205194

—〇, I 1 o厂〆 〇 lI o- pentaerythritol skeleton Trihydrocarbyl propane skeleton

I \〇 - dipentaerythritol skeleton sorbitol skeleton

The polymerizable compound (II) which is particularly preferable in the glycerin skeleton is one or both of four or more and six or less acryloyl fluorenyl groups or fluorenyl fluorenyl groups in the molecule, and has four or more and six molecules derived from glycidyl groups in the molecule. A compound having a radical structure and further having a pentaerythritol skeleton, a dipentaerythritol skeleton or a sorbitol skeleton as a branched structure. The polymerizable compound (II) preferably has such a structure that a branched structure has a central structure, and three or more acryloyl or methacrylic groups are present at the terminal, and one or more of the side chains are derived from glycidol. Base of the base. The following compounds are exemplified as specific examples of the polymerizable compound (II).

-16- 201205194

OH

HO

(D) The polymerizable compound further contains (III) a (meth)acryl fluorenyl group having three or more and 12 or less, in addition to the polymerizable compound of the above (I) and (II), and this (meth) The number of propylene groups is divided by -17 to 201205194. The polymerizable compound having a structure having an unsaturated group density of 0.0067 or more and 0.0114 or less and having a structure different from the above (I) and (II) (hereinafter referred to as " The polymerizable compound (III)") is preferred. Further, by further containing the polymerizable compound (III), it is possible to provide a color filter having high photothermal crosslinkability, excellent developability, and high reliability in the shape of a halogen. The following compounds are exemplified as specific examples of the polymerizable compound (III). In addition, the number indicates the unsaturated base density.

0. 00672

-18- 201205194

0 0104 0.0099 The specific polymerizable compound in the present invention may be used alone or in combination of two or more. In other words, as the specific polymerizable compound, one or more of the polymerizable compound (I) or the polymerizable compound (II) may be used, and one or more polymerizable compounds (I) may be used in combination with Two or more types of polymerizable compounds (II) or two or more types of polymerizable compounds (π) may be used as the polymerizable compound (II). In addition, as the polymerizable compound in the present invention, not only one of the polymerizable compound (1) and the polymerizable compound (11) but also a polymerizable compound different from the above-mentioned polymerizable compound may be used. The polymerization I·raw compound which is different from the specific polymerizable compound may be a polymerizable compound having at least one ethylenically unsaturated double bond. For example, there is at least one polymerizable compound having at least one terminal ethylenically unsaturated bond and having a structure different from that of a specific polymerizable compound. -19- 201205194 Description of different copolymerizable compounds Examples of copolymers The classes and classes of acrylic acid, itaconate, and guanamine compounds. Further, it is also an unsaturated amine or a thiol which is more than a non-saturated acid ester or an epoxidized acid or a hydroxy group. The compound of the above-mentioned unsaturated group-containing compound group polyol is used, and such a polymerizable compound such as an acrylate is widely used in the industrial field, and such a compound can be used without particular limitation. A chemical having, for example, a monomer, a prepolymer, that is, a dimer, a trimer, or the like, and a copolymer such as the like, is a structure different from the special polymerizable compound, preferably a precursor and a specific polymerizable monomer. And its acrylic acid, such as acrylic acid, hydrazinoic acid, etc.) or its aliphatic polyhydric alcohol compound, or nucleophilic or polyfunctional isocyanate monofunctional or polyfunctional isocyanic acid vinegar or amine A reactant, a polyfunctional alcohol, an example, and a specific example (III) of styrene and ethylene can be used. Further, the polymerizable compound of 4 may be an electrophilic property such as unsaturated acid, crotonic acid, or preferably a non-saturated citric acid and an addition reaction having a hydroxycarboxylic acid ester or a guanamine. Substituted functional alcohols, substituted amines having an imide group carboxylic acid ester or decylamine, and carboxylic acid substituted groups. The compound and the unsaturated carboxyl group are known as ethylene glycol. In this particular compound, oligomers or forms. The polymerizable compound I uses two or more kinds of compounds. And carboxylic acids (for example, isocrotonic acid, equine saturated carboxylic acid and aliphatic aliphatic polyamine or amine groups, sparse and monofunctional products, and specific materials. Also preferred is unsaturated, thiol Or a toluene sulfonate and a monofunctional or. In addition, other unsaturated phosphonic acid, acid esters of monoacrylic acid S, three-20-201205194 ethylene glycol diacrylate, 1,3 - butyl Alcohol diacrylate, 1,4-butanediol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl propyl) Ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl Tetraol triacrylate, neopentyl alcohol tetrapropane acid, dipentaerythritol diacrylic acid S, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol Pentaacrylate, sorbitol hexaacrylate, tris(propylene oxyethyl) iso-cyanide Ester, polyester acrylate oligomer, isomeric cyanuric acid EO modified tripropylene vinegar, etc. The mercapto acrylates are 1,4-butanediol dimercapto acrylate, triethylene glycol II Methacrylate, neopentyl glycol dimercapto acrylate, trihydrocarbyl propane trimethacrylate, trimethylolethane tridecyl acrylate, ethylene glycol dimercapto acrylate, 1 , 3-butanediol dimercapto acrylate, hexanediol dimercapto acrylate, neopentyl alcohol dimercapto acrylate, neopentyl alcohol tridecyl acrylate, neopentyl alcohol tetradecyl acrylate , dipentaerythritol dimercapto acrylate, dipentaerythritol hexamethylene acrylate, sorbitol tridecyl acrylate, sorbitol tetradecyl acrylate, bis [p-(3-methacryl oxime) Oxy-2-hydroxypropoxy)phenyl]didecyldecane, bis-[p-(mercaptopropenyloxyethoxy)phenyl]dimethylnonane, etc. Ethylene glycol diitaric acid ester, propylene glycol II itaconate, 1,3-butylene glycol isaconate, 1,4-butanediol diitaconate, 201205194 pentaerythritol Acid ester, Yamanashi Four itaconate esters, etc. crotonate has ethyl alcohol dicrotonate s, sputum, 4 • butanediol dicrotonate, pentaerythritol dicrotonate, mountain plow, rice, tetradecylate, etc. The isocrotonate is ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. The maleate ester has ethylene glycol dimaleate, Triethylene glycol dimaleate, neopentyl alcohol dimaleate, sorbitol tetramaleate, etc. Other examples of self-contained species, preferably used, for example, Japanese Patent Publication No. 5 1 -47 3 Japanese Patent Publication No. 4, pp. The aromatic group-containing one described in the publication of the Japanese Patent Publication No. Hei No. Hei. Further, the above ester monomers may also be used as a mixture. Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis acrylamide, methylene bis methacrylamide, and 1,6-hexamethylene double. Acrylamide, iota, 6-hexamethylene bis-decyl acrylamide, diethylene triamine tripropylene decylamine, benzodiazepine bis acrylamide, benzodiazepine bis methacrylamide, and the like. Other examples of the preferred amide-based monomer include those having a cyclohexene structure as described in Japanese Patent Publication No. 5 4-2 1726. Further, the amino acid formic acid produced by the addition reaction of an isocyanate and a hydroxyl group is preferably an addition polymerizable compound, and the vinylamino group described in, for example, Japanese Patent Publication No. Sho 48-4 1 708 In the case of a formic acid vinegar compound or the like, the vinylamino-based acid ester compound is a vinyl group-containing ethylene compound represented by the following general formula (IV) in a polyisocyanate compound having two -22 to 201205194 or more isocyanate groups in one molecule. The monomer contains two or more polymerizable vinyl groups in one molecule formed, and the formula (IV) CH2=C(R4)COOCH2CH(R5)OH(iv) (except that R4 and R5 each independently represent η or CH3 ). Further, it is preferably an acrylic acid S, which is described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. Ethylene oxide system described in Japanese Patent Publication No. Sho. No. 5-6-86, No. Amino acid phthalate compounds of the backbone. In addition, an addition of an amine structure or a thioether structure in the molecule described in JP-A-63-260909, JP-A-63-260909, and JP-A No. Hei. A photocurable coloring composition having an excellent photospeed can be obtained by using a polymerizable compound. Other examples can be cited as described in the publications of the Japanese Patent Publication No. Sho. No. Sho 49-43 1 8 3, the Japanese Patent Publication No. Sho 49-43 1 9 1 and the Japanese Patent Publication No. 52-30490. A multifunctional acrylate or methacrylic acid such as an epoxy acrylate obtained by reacting an ester acrylate or an epoxy resin with (fluorenyl) acrylic acid is cool. In addition, the specific unsaturated compound described in Japanese Patent Publication No. Hei 4-40337, and the Japanese Patent Publication No. Hei. A vinylphosphonic acid-based compound described in the publication -25493. Further, it is preferable to use a perfluoroalkyl group-containing structure described in JP-A-61-22048. Further, -23-201205194 and ' can also be used as photocurable monomers and oligomers in Japanese Association Association v.l.20, Νο. 7,300~3 08 (1984). From the above viewpoints, bisphenol quinone diacrylate, bisphenol fluorene diacrylate Ε Ο modified body, trihydroxy decyl propylene triacrylate, trishydroxy propyl propyl triacetate (acrylonitrile propylene hydride) can be exemplified. Base, listening, trimethyl ketone triacetate, tetraethylene glycol dipropion acid, neopentyl alcohol dipropionic acid S, pentaerythritol triacrylate, neopentyl alcohol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene fluorene) Oxyethyl) isomeric cyanurate, neopentyl alcohol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified body, etc. are preferable. Further, it is preferably a commercially available product. Aurethane oligomer UAS-10, UAB-140 (manufactured by Sakamoto Paper Chemical Co., Ltd.), DPHA (manufactured by Sakamoto Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, 1'-600, person 1-600 (shared company). Among them, bisphenol A diacrylate EO modified body, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate 'three (propylene)醯 oxyethyl) iso-cyanuric acid vinegar, neopentyl alcohol tetraacrylate E0 modified body, dipentaerythritol hexaacrylate EO modified body, etc., and the commercial product thereof is preferably DpHA (Japanese chemical) Company system), UA-306H, UA-306T, UA-3061, AH-600, T-600, AI-600 (Kongrong Chemical Industry Co., Ltd.). (D) The content of the polymerizable compound is preferably from 5% by mass to 55% by mass, more preferably from 1% by mass to 50% by mass, based on the total nonvolatile matter in the photocurable coloring composition of the present invention. 'More preferably 1 5 mass ❶ ~ 45 mass%. &quot;24- 201205194 When the amount of the polymerizable compound used is in this range, the desired chromaticity, luminance, and film thickness are easily obtained, and the shapes of the pixels and the contact holes are also good. In addition, the total content of the polymerizable compound (1) and the polymerizable compound (II) in the polymerizable compound is preferably 5% by mass to 95% by mass, preferably 30% by mass to 70% by mass, based on the mass. . In addition, the total non-volatile content of the photocurable coloring composition in the present invention means the total content of all the components of the photocurable coloring composition other than the solvent (A) constituting the photocurable coloring composition, and forms a color. In the case of a filter, it generally means the content of the component which comprises a photocurable coloring composition layer after drying. Further, the polymerizable compound (111) is preferably contained in the (D) polymerizable compound in an amount of, for example, 5% by mass to 8% by mass, preferably 2% by mass to 60% by mass. When a polymerizable compound (ΠΙ) is contained in this range, a photocurable coloring composition having high photothermal crosslinkability, excellent developability, and excellent shape of a halogen can be obtained. &lt;(Β) Pigment&gt; The photocurable coloring composition of the present invention contains at least one (Β) pigment. The (Β) pigment may be an inorganic pigment or an organic pigment, and it is preferable to use a particle size as small as possible from the viewpoint of high transmittance. The average value of the secondary particle size is Ο.ΟΙμιη~〇.1μηι, more preferably 〇1μιη~〇 The range of the claws. In the photocurable coloring composition of the present invention, even when the pigment particle size is small, the dispersibility and the dispersion stability are good, and thus the color purity is excellent, the hue is good, and the color reproducibility is good. Further, in the present invention, the pigment contained in the 'photocurable coloring composition is less than the total amount of the pigment in the total amount of the pigment having a primary particle diameter of less than pm2 pm. 10%, and the ratio of the pigment having a primary particle diameter exceeding 0 08 μπ1 is preferably less than 5 〇 / 0 in the total amount of the pigment. The ratio of the pigment having a primary particle diameter of less than 0.02 μη is less than 1%, and the heat resistance is good, and Preventing the change of chromaticity; making the ratio of the pigment having a primary particle diameter exceeding 〇〇8^坩 less than 5%, the contrast stability of the photocurable coloring composition is good, and the malfunction of the foreign matter is prevented. The ratio of the pigment of 0.02 μηι is more preferably less than 5% from the viewpoint of heat resistance and prevention of change in chromaticity. The ratio of the pigment having a primary particle diameter exceeding 0·08 μϊη is more preferably less than 3 from the viewpoint of improvement of contrast. /〇. The primary particle size of the pigment can be measured using ΤΕΜ (transmission electron microscope). At this time, the ITEM photo is image-analyzed and the particle size distribution is investigated. For example, by measuring all the observed samples at 3 to 100,000 times. The number of particles and the number of particles smaller than, and more than 0.08, the particle size distribution. More specifically, the pigment powder is observed under a transmission electron microscope at 30,000 to 10,000 times and photographed, and then measured. : The ratio of the primary particles of less than ~, ... 0·0 is determined by the length of the primary particles. The position of the pigment powder is changed, and the operation is performed on the two spaces in total and the results are averaged. (B) The inorganic pigment of the pigment may, for example, be a metal compound such as a gold salt, or a composite oxide of a metal such as copper, titanium, magnesium, chromium, or rhyme, etc. The oxide of the above, and the aforementioned metal -26-201205194 Further, the aforementioned organic pigment which can be used as the (B) pigment can be exemplified by 匸·工色红1, 1, 2, 4, 5, 6, 7, 9 , 1〇, 14, 17, 22, 23, 31, 38, 4 Bu 48:1, 48:2 , 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81: 1 , 81: 2, 81: 3, 83, 88' 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171' 172, 175, 176 , 177, 178, 179, 184, 185, 187' 188, 190' 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264' 270 ' 272 ' 279 ; CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10' 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40' 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 1〇4 &gt; 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128 , 129 &gt; 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164 , 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214; CI Pigment orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73; CI Pigment Green 7, 10, 36, 37, 58; -27- 201205194 C_I. Pigment Blue ι, 2, 15, 15: 1, 15 · 2, 15. 3, 15: 4, 15: 6, 16, 22 The Cl substituents of 60, 64, 66, 79, and 79 are changed to 〇Η, 80; CI pigment violet 1, 19, 23, 27, 32, 37, 42; CI pigment brown 25, 28, and the like. Among the pigments which can be preferably used among these, the following are exemplified. However, the present invention is not limited to this. CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; C · I. Pigment Orange 3 6 , 7 1 ; CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264; CI·Pigment Violet 19, 23, 32; 6, 16, 22 '60, 66; CI Pigment Blue 1 5 : 1, 1 5 : 3, 1 5 C · I _ Pigment Green 7, 3 6, 3 7, 5 8. The photocurable coloring composition of the present invention is preferably used for the formation of blue colored pixels, and the effects of the present invention can be satisfactorily exhibited. Anthraquinone blue pigment for blue has high absorbance in the ultraviolet region and is not easy

The effect of the invention.

It is excellent in heat resistance, light resistance, and contrast, and C. I. Pigment Blue 1 is the same as 15:4, and 15:6, and C.I. Pigment Blue 15: 6 ' can be more preferably used. -28-201205194 The content ratio of the anthrain-based blue pigment in the total of the (B) pigment used in the photocurable coloring composition of the present invention is preferably 5% by mass or more. When the ratio of all the pigments of the relative anthraquinone-based blue pigment is 50% by mass or more, high heat resistance, light resistance, and contrast enthalpy can be obtained. Further, the photocurable coloring composition of the present invention preferably contains a purple pigment as a pigment for chromaticity adjustment in addition to the above-described anthraquinone-based blue pigment. Contains a purple pigment to provide a deep blue color with a high NTSC ratio (color saturation). As the purple pigment, C.I. Pigment Violet 19, 23, and 32 can be used. Among them, C.I. Pigment Violet 23 is preferred from the viewpoints of obtainable luminance, light resistance, heat resistance, and high contrast. (B) The amount of the pigment to be added to the photocurable coloring composition can be appropriately selected from the desired color, brightness, and film thickness, but is preferably 5 mass based on the total nonvolatile matter (total solid content other than the solvent). The range of % or more and 50% by mass or less is more preferably 10% by mass or more and 40% by mass or less, and still more preferably 15% by mass or more and 3 % by mass or less. (B) If the amount of the pigment added is in this range, the desired color, luminance, and film thickness are easily obtained, and the shape of the halogen or the contact hole is also good. The total non-volatile content of the photocurable coloring composition in the present invention means the total content of all the components of the photocurable coloring composition other than the solvent (A) constituting the photocurable coloring composition, and the color filter is formed. In the case of a light sheet, 'generally means the content of the component constituting the photocurable coloring composition layer after drying. -29- 201205194 (coated pigment) In the present invention, it is particularly preferable to use an organic pigment as a (Β) pigment and a pigment.

_ * &quot; 4π initial coating pigment, this pigment is in the micro

The above-mentioned coated molecular compound may be coated with a pigment as described later (Ε), and then the pigment may be coated with the finely divided pigment, and the formation of secondary aggregates may be suppressed to be dispersed in the state of primary particles. In other words, the coating pigment has an improved dispersibility and is excellent in dispersion stability of the primary particles which can stably maintain dispersion. For the coating method of the polymer compound or the pigment for coating the pigment, the treatment method and the polymer compound described in paragraphs [0025] to [〇〇78] of JP-A-2009-144 1269 are more preferably used. Further, in the present invention, at least one type of pigment is dispersed in a dispersant, and it is preferably used as a pigment dispersion composition. The same applies to the use of the coated pigment as described above. The dispersing agent can be used to increase the dispersibility of the pigment. For example, a conventional pigment dispersant or a surfactant may be appropriately selected as a dispersant. Specifically, a plurality of compounds can be used as the dispersing agent, and examples thereof include an organic siloxane polymer ΚΡ341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic (co)polymer Polyflow Νο. 75, Ν〇· 90, Νο·95 (Kongrong Chemical Industry Co., Ltd.), WOO 1 (Yu Shang (share) -30- 201205194 system) and other cationic surfactants; lauryl ethoxylate, stearyl alcohol Polyoxyethylene ether, oleic acid polyoxyethylene ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbus Nonionic surfactant such as alcoholic anhydride fatty acid ester; anionic surfactant such as W004, W005, W017 (manufactured by Yusei Co., Ltd.); EFKA-46 'EFKA-47, EFKA-47EA, EFKA Polymer 100, Polymer dispersion agents such as EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Ciba Speciality Chemical), DISPERSE AID6, DISPERSE AID8, DISPERSE AID15, DISPERSE AID9100 (all manufactured by SAN NOPCO); Solsperse 3000, 5000 , 9000, 1 2000, 1 3240, 13940, 17000 '24000, 26000 ' 28000 and other Solsperse dispersants (manufactured by Sakamoto Lubrizol Co., Ltd.); ADEKA Pluronic L 31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 , F87, P94, L101, P103, F108, L121, P-123 (Asahi Kasei Co., Ltd.) and Eonet S-20 (Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174 '176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by BYK-CHEMIE Co., Ltd.). Other examples include oligomers or polymers having a polar group at a molecular terminal or a side chain such as an acrylic copolymer. The content of the dispersant is preferably from 1% by mass to 100% by mass, more preferably from 3% by mass to 70% by mass based on the mass of the (B) pigment. -3 1- 201205194 Adding (B) pigment to photocurable coloring is preferred in terms of pigment dispersibility, and it is preferable to blend the pigment dispersion composition containing the agent at the time of preparation. Add pigment derivatives as needed. &gt; The composition of the knife is such that the portion having affinity with the dispersing agent or the pigment into which the polar group is introduced is adsorbed on the surface of the pigment, and the pigment is adsorbed by the microparticle-shaped guillotine. Into h... dispersed in the pigment dispersion composition. (3) The photocurable coloring composition having such a pigment dispersion composition can prevent the re-agglomeration of the pigment, so that a color filter excellent in contrast and excellent in transparency can be effectively formed. The pigment derivative is specifically 凫 凫 右 * 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你A compound having an aromatic group as a substituent. Specific examples of the organic pigment of the parent skeleton include quinacridone pigments, ugly pigment pigments, azo pigments, ruthenium pigments, isoindole pigments, isoindolinones, and quinolines. Pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, and the like. Further, as the precursor skeleton, a pale yellow aromatic polycyclic compound such as a naphthalene, an anthracene, a triazabenzene or a quinoline which is not called a dye may be used. Japanese Patent Publication No. 1 1-49974, Japanese Patent Application Laid-Open No. -1 8 9 7 3 2, Japanese Patent Laid-Open No. 1 2 5 5 5 〇1, and Sakamoto Kaikai 2 0 0 6 - Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. 2005-234, pp. The above is a pigment derivative as disclosed in Japanese Laid-Open Patent Publication No. 2001-356210. -32- 201205194 The content of the pigment derivative in the pigment dispersion composition is preferably from 1% by mass to 30% by mass, more preferably from 3% by mass to 2% by mass based on the mass of the pigment. When the content is within the above range, the viscosity can be lowered while being well dispersed, and the dispersion stability after dispersion can be improved. As a result, the photocurable coloring composition containing such a pigment dispersion composition is suitable for producing a high contrast color filter having high transmittance, excellent color characteristics, and good color characteristics. The method of dispersing the pigment can be carried out by, for example, preliminarily dispersing the pigment and the dispersant in a homogenizer or the like, and the material is finely dispersed by using a bead disperser such as cerium oxide beads. [Dye] The photocurable coloring composition of the present invention can be used in combination with a dye as a coloring agent in addition to the pigment, within a range not impairing the effects of the present invention. The dye which can be used as the coloring agent is not particularly limited, and can be used as a conventional dye for use in a color light-emitting sheet. For example, Japanese Patent Laid-Open Publication No. Sho 64-90403, Japanese Patent Laid-Open No. Hei 64-91102, Japanese Patent Laid-Open No. Hei 1-94301, Sakamoto Kaikai 6-1 1614, Sakamoto Teden 2592207, USA Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, U.S. Patent No. 5,333,500, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei 6- 1 948 828, Japanese Patent Laid-Open No. Hei 8-21 1 599, Japanese Patent Laid-Open No. Hei 4-249-5 49, Japanese Patent Laid-Open No. Hei 10-1233 No. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaiping 8- 1462 1 A, Japanese Unexamined H-343437, 曰本特开平8·62416, JP-A-2002-14220, JP-A-2002-14221, and Japan Japanese Patent Publication No. 2002-14222, Japanese Patent Laid-Open Publication No. 2002-14223, Japan The pigments described in JP-A-H08-302224, JP-A-H8-73758, JP-A-8-179120, and JP-A-8-1 5 1 53 1 and the like. In terms of chemical structure, a pyrazoleazo system, an anilinozo system, a triphenylsulfonium system, a brewing system, and a ruthenium ratio can be used. Anthrapyridone, benzylidene, Oxonol (Fuji exclusive dye), pyrazoltriazoleazo, pyridinazole (pyrid〇neaz〇), Sainen (cyanine) bismuth, thiophene thiazine, phlox and 0 ratio. The dye is a dye such as a quinone imine, a xanthene, an anthraquinone, a benzopyran or an indig. &lt;(A) Organic solvent&gt; The photocurability of the present invention is known to be &, and the product can be prepared using a general solvent. Further, the above-mentioned pigment dispersion* is formed into a makeup, and the product can be prepared by using a solvent. In the organic solvent to be used in the present invention, the boiling point is 1 1 〇C or more and 200 ° C or less, and the applicability, the suppression of the nozzle clogging at the time of coating, and the solvent removal property at the time of forming the vocal ruth It is better. The hydrazine layer is bathed into the organic solution 7 7 X X -r ^ which can be used in the present invention. The esters are, for example, ethyl acetate, succinyl sulphate, isobutyl sulphate, 7 ng, armor酉文戍S日, Isoamyl acetate, I, I, I, Isopropyl, Isopropyl, butyl, butyrate, alkyl ester, milk, butyl s西曰礼西夂甲, lactic acid, oxyacetic acid-34- 201205194 decyl ester, ethyl oxyacetate, butyl oxyacetate, methoxy methoxyacetate, ethyl methoxyacetate, methoxy a 3-methoxypropionic acid alkyl ester such as butyl acetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, methyl 3-oxypropionate or ethyl 3-oxypropionate (for example, 3) - decyloxypropionate, ethyl 3-methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), methyl 2-oxypropionate, Ethyl 2-oxopropionate such as ethyl 2-oxypropionate or propyl 2-oxypropionate (for example, 2-nonoxypropionic acid ethyl ester, 2-methoxyoxypropionate ethyl ester, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2-methylpropionic acid Ester, ethyl 2-oxo-2-mercaptopropionate, decyl 2-methoxy-2-mercaptopropionate, ethyl 2-ethoxy-2-mercaptopropionate, etc., and acetone Acid ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-ketobutyrate, ethyl 2-ketobutyrate, 1,3 - dibutyl Alcohol diacetate, etc.; &amp; class I, such as diethylene glycol dimethyl ether, tetrahydro-m-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoterpene ether, two Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol oxime ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether An acid ester, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tripropylene glycol mono-n-butyl ether, tripropylene glycol methyl ether acetate, etc.; acetone, Ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; -35- 201205194 Alcohols such as ethanol, 1, propanol, propylene glycol oxime ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl _; Tobacco members, such as A stupid, .LL ^, - 曱 Ben 4. In this special case, it is preferably 3, 7 ^ acid vinegar, acetoacetate, bis, propyl propionate sl oxypropoxy propionate,: alcohol, dimethyl mystery, butyl vinegar, 3 -Methyl butyl carbitol acetic acid cool two: hexanyl, ethyl carbitol acetate vinegar,

Propyl alcohol ethyl acetate acetate and the like.叼^ T The refrigerant is used alone or in addition to the photocurable composition of the present invention. The amount of the organic solvent in the amount of 邾曰 amp &amp; + color and (A) organic solvent Depending on the purpose, the non-volatile coloring composition is not volatilized = the viewpoint of applicability is &quot;hardening %~30% by mass is the concentration of the knives to prepare 1 〇 mass (C) photopolymerization initiator> In the present invention The photocurable initiator is a compound containing (c) a photopolymer which is decomposed by light, (9) a polymerizable compound, and which promotes polymerization. In order to polymerize at the wavelength of ultraviolet rays in the absorbers, L has a sensitivity at the wavelength of ultraviolet rays. Further, the light:: agents may be used singly or in combination of two or more. The photopolymerization initiator to be used may, for example, be an organic ketal I or an oxygen bis. sit (—π10 compound, a few compound, oxime, benzoin compound... acridine compound, organic overgasification 201205194 compound, even Nitrogen compounds, coumarin compounds, azides, gold Compounds, hexaaryl laugh flavor compounds, rotten organic acid compounds, disulfonic acid compounds, oxime ester compounds, salts of compounds Bin, acyl oxide scales compounds. The organic halogenated compounds specifically include the Wakabayashi et al., "Buii

Chem. Soc Japan, 42, 2924 (1969), U.S. Patent No. 3,9,5,815, Japanese Patent Publication No. Sho 46-4605, Japanese Patent Laid-Open No. Sho 48-3 628 No. 1, Japanese Patent Laid-Open No. 55-32070 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.昭 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 The compound described in (1970), etc., may specifically be a tridentate methyl-substituted oxazole compound or an s-triazabenzene compound. The carbonyl compound may, for example, be benzophenone, benzyl ketone or 2- Mercaptobenzophenone, 3-methyldibenzophenone, 4-methyldibenzophenone, 2-gasbenzophenone, 4-bromodibenzophenone, 2-carboxybenzophenone, etc. Benzophenone derivatives; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, hydroxycyclohexyl phenyl ketone, α-hydroxy-2-indole Phenyl phenylacetone, 1-hydroxy-diphenyl Base-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl)one, 2-methyl-1-(4'-(indolylthio)phenyl)-2 - 淋淋_1_ propyl hydrazine, 2-phenylhydrazino-2-didecylamine-1-(4-morphinylphenyl)-butyrol-1,2,4,6-trimethylphenyl fluorenyl- Acetophenone such as diphenyl-phosphine oxide, 1,1,1-tris-methyl-(p-butylphenyl) ketone, 2-phenylindenyl-2-didecylamine-4-morpholinphenone -37- 201205194 Derivatives; xanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-oxothioxanthone, 2,4-dimercaptothioxanthone, 2,4· Diethyl thioxanthone, 2,4-diisopropyl thioxan i thioxanthone derivative; benzoic acid ester derivative such as p-diamine benzoic acid ethyl ester, p-diethylamine benzoic acid ethyl ester, and the like. The hexaaryldiimidazole compound may, for example, be a compound described in each specification such as Japanese Patent Publication No. Hei 6-29285, U.S. Patent No. 3,479,185, the same as No. 4,311,783, and No. 4,622,286. Specifically, 2,2'-bis(indolyl-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2,-bis(indolyl-bromophenyl)-4, 4',5,5,-tetraphenyldiimidazole, 2,2 - double (ο,ρ·一气本基)_4,4,5,5'-tetraphenyl 2d m. Sit, 2,2'-bis (〇-gas phenyl) -4,4',5, 5'-tetrakis(111-decyloxyphenyl)diimidazole, 2,2,-bis(indole, fluorene,-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(〇-nitrophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2,-bis(〇-methylphenyl)-4,4' , 5,5 tetraphenyldiimidazole, 2,2,-bis(indole-trifluorophenyl)-4,4',5,5'-tetraphenyldiimene. Wait and wait. The oxime ester compound ' can be exemplified by JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1 995) 202-232, 曰本特开2 0 0 0 - The compound described in the publication No. 6 6 3 8 5, the compound described in JP-A-2000-80068, and JP-A-2004-534797. As a specific example, Irgacure OXE-O 1, OXE-02, etc., manufactured by Ciba Speciality Chemical Co., Ltd. are preferable. Among these, 'as a photopolymerization initiator, from the viewpoint of exposure sensitivity' is preferably selected from the group consisting of a tridentate methyltriazabenzene compound, a benzyldidecyl ketal compound, and an α-hydroxyketone compound. , α-amino ketone compound, decyl phosphine compound 'phosphine oxide compound, metallocene compound, -38- 201205194 oxime ester compound, two penganyl-aryl imidazole-jujube, 7 azole compound, _~~ l, bismuth compound, benzothiazepine P 嗣 斗 derivative, Cyclopentan _ ^ Μ S, acetophenone-based compound and its mono-benzene-iron eight &amp; „ u compound, 3-娑| ^ 错 &amp; and its salt, halosulfonyl oxadiazole

7 is a compound selected from the group consisting of human, _, and chemical. The ketone compound, the 酼*3-halomethyltriazabenzene compound, the α-amine-violet lining, the compound, the triaryl phthalate, the gasified phosphine compound, and the compound. Γ:::: The group rust-based compound and the diphenyl hydrazine-based system are at least one compound selected from the group consisting of ternary groups, the best compound, the oxime ester-based human stagnation compound, (X) - an aminoketone compound 1C* 5 compound, at least one π azole dimer of a group of triads, and a benzophenone-based J main compound). The present invention t is preferably a fatty acid compound represented by the formula (5), which is an oxime ester compound having the following 诵-V r ± not s initiator.

"or8 (5) L n O 〇V^q2 〆SAr In the above formula (5), R8 and p each independently represent a - substituent "Q and Q2 each independently represent a binary organic group, and Ar represents an aryl group. n is a positive number of 〇 5. When a plurality of p are present, each of the plurality of p independently represents a mono-substituent. The photopolymerization initiator which can be preferably used in the photocurable coloring composition of the present invention is 曰本特开2 The compound of the above formula (5) used in the present invention has an absorption wavelength in a wavelength region of from 250 nm to 500 nm. The compound of the above formula (5) used in the present invention has an absorption wavelength of from [0089] to [0173]. In the case of the person 1 king, the absorption wavelength is in the wavelength range of 300 nm to 380 nm. The absorbance of the 308 nm and 355 nm is particularly high. The (C) light is preferably in the relative photocurable coloring composition. The total non-volatile content, the content of the polymerization initiator, is preferably 〇·丨% by mass to 2〇% by mass, 〇·5 mass% to 15% by mass, particularly preferably 3% by mass to 15% by mass. 'Good sensitivity and pattern formation are obtained. [Sensitizing dye] Photocurable coloring in the present invention In the case of improving the sensitivity, it is preferable to add a sensitizing dye. The exposure of the wavelength at which the sensitizing dye can absorb can promote the radical generating reaction of the photopolymerization initiator component, or The polymerization reaction of the polymerizable compound carried out by the reaction. Such a sensitizing dye may, for example, be a dye or a pigment which is conventionally classified as a photosensitizing dye or dye, or which absorbs light and interacts with a photopolymerization initiator. The sensitizing dye, preferably the photosensitizing dye or dye, may be exemplified by polycyclic aromatics (for example, 芘'茈, extended triphenyl), xanthene (such as luciferin, eosin, erythrosine). , Rhodamine B, Bengal rose), cyan (such as thiacarb 〇cyanine, oxacarbocyanine), merocyanine (such as merocyanine, carbon merocyanine (carbomerocyanine) )), ° sputum (such as sulphur, indigo, toluidine blue), acridine (such as acridine orange, chlorpyridinium, acridine yellow), anthraquinones (such as anthraquinone, Metal anthraquinone), porphyrins (eg Phenyl porphyrin, central metal substituted porphyrin), chlorophyll (eg chlorophyll, chlorophyllin, central metal substituted chlorophyll), gold-40- 201205194 is a complex, steroid (such as strontium), squaric acid Squarylium (for example, squaric acid rust salt), etc. Examples of the more preferred photosensitizing dye or dye are exemplified below. The styrene-based dye described in JP-A-37-13034; The cationic dye described in Japanese Patent Publication No. 62-143044; quinoxalinium salt described in Japanese Patent Publication No. 59-24147; Japanese Patent Application Laid-Open No. Hei 64-33104 The new methylene blue compound; the scorpion oxime dye described in Japanese Patent Laid-Open No. Hei 64-56767; (匕6112(^31^116116 dye); the acridines described in Japanese Laid-Open Patent Publication No. Hei No. 2-226148, and the Japanese Patent Publication No. Hei 2-226149; Salt; the green type described in Japanese Patent Publication No. 46-42363; Level 2 - Ben 6305 3 described Bing squeak. The conjugated ketone dye of the Japanese Patent Laid-Open Publication No. Hei 2- 21858 The azocinnamylidene derivative described in the publication No. 1; the phthalocyanine dye described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 62-31 844, 曰本特The diphenylsulfonium-based dye described in Japanese Patent Publication No. Sho 62-143043, and the aminostyryl ketone described in JP-A-59-28325; A coloring matter described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The cyanine pigment described in the publication of the Gaza No. 5 9 - 8 9 3 0 3 - 41 - 201205194 曰 曰 特 特 8 8 8 -1 2 9 2 5 7 A benzopyrene-based dye described in JP-A-8-334897. Other preferred embodiments of the sensitizing dye include the following dyes which belong to the following compound group and have a maximum absorption wavelength from 35 Å to 45 Å. Examples thereof include polycyclic aromatics (for example, ruthenium, osmium, and terphenyl), gargles (for example, luciferin, eosin, erythrosine, rhodamine B, bengal rose), and cyan (for example, thiocarbon). Cyanine, chloroform, chloroforms Acridine yellow, acridine yellow), fungi (such as strontium), squaric acid rust salts (such as squaraine rust salts). The content of the sensitizing colorant in the total photo-curable coloring composition is preferably from 质量% by mass to 20% by mass, more preferably from 5% by mass to 15% by mass. /〇. [Bulk compound] The thiol compound preferably contains a photocurable coloring composition in the present invention. The thiol compound in the present invention acts to improve the sensitivity of the formed color book, or to exhibit the adhesion, and to enhance the adhesion of the sensitizing dye or photopolymerization; Or inhibiting the effects of polymerization and the like. The polymerization inhibitor thiol compound can be exemplified by bis(EGTP), dithiomethine- γ 0 wenyi- xixi propyl propyl &amp; butyl alcohol (BDTP), propylene Thiopropionate (TMTp) - samarium, tetrasyl propionate, neopentyl ester-42-201205194 (ΡΕΤΡ), thiol propionic acid derivative such as THEIC-BMPA represented by the following formula; Ethyl Alcoholate (EGTG), Butane Ethyl Ethyl Ester (BDTG), Diethyl Ethyl Hexane Ethyl Ester (HDTG), Trimethylolpropane Triethylene Sulfate (TMTG) Ethylene glycolic acid derivatives such as tetraethyl thiolate neopentyl ester (PETG); 1,2-benzenedithiol, 1,3-benzenedithiol, 1,2-ethanedithiol, 1 , 3-propanedithiol, 1,6-hexanedithiol, 2,2'-(ethanedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, p-nonylbenzene Mercaptans such as dithiol and m-diphenylene dithiol; and oxime ethers such as diterpene ether. These may be used alone or in combination of two or more. 〇

II

C hsc2h4cooc2h4i^, ijic2h4ococ2h4sh ο=α xc=o HSC2H4COOC2HiN/

THE I C - BMPA The thiol compound used in the present invention is preferably represented by the following formula (I). General formula (I)

-43 201205194 In the formula (I), 'R represents a hydrogen atom, an alkyl group or an aryl group, and A represents an atomic group which forms a hetero ring together with N == C-N. In the formula (I), 'r' represents a hydrogen atom, a hospital group or an aryl group. The alkyl group represented by the anaesthesia may, for example, be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably a linear one having a carbon number i to i 2 and a carbon number of 3 to i. a branched chain of 2 and a cyclic alkyl group having 5 to 5 carbon atoms. Specific examples thereof may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, Hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, secondary butyl, tert-butyl, isopentyl, neopentyl, indoleyl butyl, isohexyl , 2-ethylhexyl, 2·methylhexyl, cyclohexyl, cyclopentyl, 2-reductive, and the like. In addition to the monocyclic structure of the aryl group represented by R, one to three benzene rings may be exemplified to form a fused ring, and a benzene ring and a five-membered unsaturated ring may form a fused ring. Specific examples may be exemplified. A group, a naphthyl group, a phenanthryl group, a fluorenyl group, a dihydroindenyl group, a fluorenyl group, etc., among these, a phenyl group and a naphthyl group are preferable. These alkyl or aryl groups may further have a substituent, and the substituent which may be introduced may, for example, be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a direct bond which hinders an atomic number of 2 to 20. a branched, branched or cyclic alkenyl group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a fluorenyl group having a carbon number of 丨 ❻, and a carbon number of 2 to 20 An oxycarbonyloxy group, an aryloxyoxy group having 7 to 20 carbon atoms, an aminomethyl methoxy group having 1 to 20 carbon atoms, a carboguanamine group having 1 to 20 carbon atoms, and a carbon number a sulfonylamino group of 1 to 20, an amino fluorenyl group having 1 to 20 carbon atoms, an amine sulfonyl group, a substituted sulfonyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms Aryl-44-201205194 having a carbon number of 6 to 20, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an N-alkenylamine having 1 to 20 carbon atoms. a sulfonyl group, an N-amine sulfonylaminomethyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having a carbon number of 丨~2〇, an arylsulfonyl group having 6 to 20 carbon atoms, and carbon Alkoxycarbonylamino group having 2 to 20 atomic number, aryloxycarbonyl group having 7 to 20 carbon atoms Amino group, amine group, substituted carbon group of 丨~", imine group having 1 to 20 carbon atoms, ammonium group having 3 to 20 carbon atoms, carboxyl group, sulfonic acid group, oxy group, fluorenyl group, carbon The alkylsulfinyl group having 1 to 2 fluorene, the arylsulfinyl group having 6 to 20 carbon atoms, the alkylthio group having a carbon number, the arylthio group having 6 to 20 carbon atoms, and the number of carbon atoms 〇 〇 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 ί ί ί ί ί ί ί ί ί 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣a group having a carbon number of 2 to 20, an isocyanate group, an isocyanate group, an isonitrile group, a halogen atom (for example, a fluorine atom, a gas atom, a bromine atom, etc.), a cyano group, a nitro group, a rust group, etc. In the case of I), Α represents an atomic group which forms a heterocyclic ring together with n=CN. The atom constituting the atomic group may, for example, be a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom or a γ atom, etc. The heterocyclic ring formed by N = CN may further have a substituent. The acceptable substituent may be the same as the substituent which may lead to the above-mentioned alkyl or aryl group. Further, sulfur S? '[Tau] [tau] more preferably gamma], Shang, two people Shu W Yu Bu general formula ([pi]) or formula (III) compound represented -45-201205194 formula (II) formula (III)

N

SH

N-Nr^N-&lt;K1X N

X

SH In the formula (II), 'R1 represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an aryl group. In the formula (III), 'R2 represents a alkyl group or an aryl group, and χ represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an aryl group. In the general formula (II) and the general formula (III), the _ atom represented by X is preferably a deficient atom, a chlorine atom, a bromine atom or a ruthenium atom. In the general formula (II) and the general formula (III), the alkoxy group and the aryloxy group represented by X may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or a pentyloxy group. , hexyloxy, dodecyloxy, benzomethoxy, allyloxy, ethoxyphenyl, carboxyethoxy, oxiranyloxyethoxy, ethoxycarbonylethoxy, decyloxy Oxyl, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, morpholinylethoxy, morpholinylpropoxy, allyloxyethoxy Ethyl ethoxy, phenoxy, nonylphenoxy, dinonylphenoxy, 2,4,6-triphenylphenoxy, isopropylphenoxy, methoxyphenyloxy, ethoxybenzene Alkoxy group, gas phenyloxy group, bromophenyloxy group, ethoxycarbonyl group, benzoquinoneoxy group, naphthyloxy group and the like. The alkyl group represented by R2 or χ in the formula (Π) and the formula (111) is synonymous with the group represented by R in the formula (I), and the preferred range is also the same. Further, in the formula (II) and the formula (III), the aryl group represented by Ri'R2 or X is independently the same as the aryl group represented by R of the formula (I), and is preferably. The scope is the same. In the general formula (II) and the general formula (III), each group represented by Ri'R2 or X may further have a substituent, and the substituent is exemplified as being introduceable to R represented by the general formula (I). The substituents of the alkyl or aryl group are the same. In the general formula (II) and the general formula (III), when X is a hydrogen atom, it is preferred from the viewpoint of solubility of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA). When 'R1 is a phenyl group in the formula (II), it is most preferable from the viewpoint of sensitivity and PGMEA solubility. In the general formula (III), when R2 is a methyl group, an ethyl group, a phenyl group or a tolyl group, it is preferably from the viewpoint of sensitivity and PGMEA solubility. Among the compounds represented by the formula (Π) and the compound represented by the formula (ΠΙ), the compound represented by the formula (ΠΙ) is preferred from the viewpoint of PGMEA solubility. These thiol compounds can be synthesized by the method described in J. Appl. Chem., 34, 2203-2207 (1961). In the photocurable coloring composition of the present invention, the compound represented by the formula (II) may be used alone or in combination of two or more kinds, and a compound selected from the compounds represented by the formula (II) may be used in combination. And a compound selected from the compounds represented by the formula (III). The content of the thiol compound in the photocurable coloring composition is preferably 〇丨% by mass to 5% by mass. More preferably 0.2% by mass to 4% by mass based on the solid content of the photocurable coloring composition. When it is in this range, it is preferable that the polymerizability of the photocurable coloring composition is not impaired. -47-201205194 &lt; (E) Adhesive> The photocurability used in the present invention = for the purpose of developing characteristics, etc., and (E) = skin L can be used to test soluble resin, epoxy Resin, pigment, polymer compound such as a polymer dispersant. When it comes to the test of "B Master &amp;&amp;&amp; Master, the best, at least, it contains alkali-soluble resin. Hereinafter, the alkali-soluble resin and epoxy resin of these adhesives will be described in detail. The alkali-soluble resin used in the lunar color-curable coloring composition is a linear organic high-molecular polymer, and may have at least i molecules (preferably molecules having an acrylic copolymer or a styrene copolymer as a main chain). It is suitably selected among the soluble resins which promote alkali-soluble groups (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a thiol group, etc.). The above-mentioned alkali-soluble resin is preferably a polymer having a carboxyl group in a side chain, and is disclosed in, for example, JP-A-59-4461, JP-A-5- 3 4 3 2, and JP-A-5曱 丨 5 5 5 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 -25 Acrylic copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and an acidic cellulose derivative having a carboxylic acid group in a side chain, An acrylic copolymer such as an acid anhydride is added to a polymer having a hydroxyl group. The acid value is in the range of 20 mgKOH/g to 2 〇〇mgKOH/g, preferably 30 mgKOH/g to 180 mgKOH/g, more preferably 5 〇mgKOH/g to 150 mgKOH/g. -48- 201205194 The alkali-soluble resin used in the present invention is particularly preferably a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith. The other monomer copolymerizable with (meth)acrylic acid may, for example, be an alkyl (meth)acrylate, an aryl (mercapto)acrylate, a vinyl compound or the like. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted by a substituent. The alkyl (meth)acrylate and the aryl (meth)acrylate may, for example, be CH2 = C(R)(COOR') [wherein R represents a hydrogen atom or a methyl group, and R' represents a carbon number of 1~ The alkyl group of 8 or the aryl group of 6 to 12 carbon atoms may specifically be exemplified by (decyl) decyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Ester, (fluorenyl) isobutyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, phenyl hydrazide Ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyalkyl (meth)acrylate (alkyl group is an alkyl group having 1 to 8 carbon atoms), Hydroxyglycidyl methacrylate, tetrahydrofuranyl methacrylate, and the like. The vinyl compound may, for example, be CH2=CWR2 [wherein R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R2 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms], and specific examples thereof include styrene and α-. Mercaptostyrene, vinyl toluene, acrylonitrile, vinyl acetate, stilbene-vinylpyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. The other monomer which can be copolymerized as described above may be used singly or in combination of two or more kinds. Among them, a polyvalent copolymer containing a benzyl (meth)acrylate/(mercapto)acrylic acid copolymer or a (benzyl)acrylic acid benzyl ester/(meth)acrylic acid/other monomer is particularly preferred. Further, a resin having a polyalkylene oxide chain in a molecular side chain is also preferably used as an alkali-soluble resin. The polyalkylene oxide chain may also be a polyethylene oxide chain, a polypropylene oxide chain, a poly(1,4-butanediol) chain or the like. The end of these chains is a hydrogen atom or a linear or branched alkyl group. The number of repeating units of the polyethylene oxide chain and the polypropylene oxide chain is preferably from 1 to 20, more preferably from 2 to 12. The acrylic copolymer having a polyalkylene oxide chain in the side chain is, for example, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(methyl)acrylate, poly(ethylene glycol-propylene glycol) single ( A compound such as a methyl acrylate or the like, and a terminal which is terminated with a thiol group, preferably contains, for example, methoxypolyethylene glycol mono(meth)acrylate or ethoxypolypropylene glycol mono( An acrylic copolymer having a copolymerization component such as methyl) acrylate or methoxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate. The acrylic copolymer preferably has an acid value in the range of 20 mgKOH/g to 200 mgKOH/g as described above. When the acid value is 200 mgKOH/g or less, the solubility of the acrylic resin to the alkali is not excessively large, and the development range (developing latitude) can be prevented from being reduced. On the other hand, as long as it is 2 〇 mg K 〇 H / g or more, the solubility in the test is not easily reduced, and the development time can be prevented from being lengthened. Further, the weight average molecular weight Mw of the acrylic resin (in terms of polystyrene converted by the GPC method) is preferably ', 〇〇〇~〗 〇〇, 〇〇〇, more preferably 3,000 to 50, 0 〇 In order to achieve a viscosity range in the step of coating or the like which is easy to use for the photocurable coloring composition, and to secure the film strength. Further, in order to improve the crosslinking efficiency which can be used for the photocurable coloring of the present invention, it is preferred to use a polymerizable group. The alkali-soluble resin having a polymerizable group may be used singly or in combination with an alkali-soluble resin having no polymerizable group. The soluble resin having a polymerizable group is preferably a polymer containing an allyl group, a (fluorenyl) acrylonitrile group or an allyloxyalkyl group as a side bond. Such an alkali-soluble resin having a polymerizable double bond can be developed in an alkaline developer, and more preferably has photocurability and thermosetting property. Among them, a resin having an allyl group as a side chain polymerizable group is preferred because it has a photoresist hardening property and a high heat decomposition resistance. Preferred examples of the alkali-soluble resin containing a polymerizable group are as follows, as long as it contains an alkali-soluble group such as a C00H group or a fluorenyl group in one molecule, and a polymerizable double bond (carbon-carbon unsaturated bond) Those who are not limited to those shown below. In other words, (1) a urethane-modified acrylic resin containing a polymerizable double bond is obtained by reacting a compound with a carboxyl group-containing acrylic resin, and the compound is previously prepared. The isocyanate group reacts with a thiol group to leave an unreacted isocyanate group and contains at least one (fluorenyl) acrylonitrile group; (2) an acrylic resin containing a carboxyl group, and an epoxy group and a polymerizable group in the molecule The unsaturated group obtained by the reaction of the double bond compound contains an acrylic resin; (3) an acid side group type epoxy acrylate resin; -5 1- 201205194 (4) an acrylic resin containing a fluorene H group and a polymerizable double The polymerizable double bond obtained by the reaction of the bond of the protonic acid anhydride contains an acrylic resin. Among the above, the resins of (1) and (2) are particularly preferred. Specific examples thereof may be those obtained by copolymerizing a monomer having a fluorene H group, such as 2-hydroxyethyl acrylate, a monomer having a c〇〇H group, such as methacrylic acid, which may be copolymerized therewith. A compound obtained by reacting a copolymer of a monomer such as a vinyl compound with a compound having an epoxy ring reactive with an OH group and a compound having a polymerizable double bond (for example, a compound such as glycidyl acrylate). In the reaction with the hydrazine H group, a compound having an acid anhydride group, an isocyanate group or a propyl group can be used in addition to the epoxy ring. Further, a compound obtained by reacting a compound having an epoxy ring described in Japanese Patent Laid-Open Publication No. Hei 6-102669, No. 6-183-8, and an unsaturated carboxylic acid such as acrylic acid can also be used. A reactant obtained by reacting with a saturated or unsaturated polyprotonic anhydride. A compound having, for example, an alkali-soluble group of a COOH group and a polymerizable double bond can be exemplified by, for example, DIANAL NR (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (polyamino phthalic acid acrylate containing COOH group) Is an oligomer, manufactured by Diamond Shamrock Co. Ltd.; VISCOAT R-264, KS RESIST 1 06 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.); CYCLOMER P series, PRAXEL CF200 series (all are Daicel Chemical Industry shares) Co., Ltd.); Ebecryl 3800 (made by Daicel-UCB Co., Ltd.). -52-201205194 The amount of the alkali-soluble resin to be used as the (E) adhesive is preferably in the range of from 3% by mass to 50% by mass, more preferably from 5% by mass to 50% by mass based on the total non-volatile content of the photocurable coloring composition. Mass %~30% by mass. When the photocurable coloring composition is prepared, it is preferred to further add an epoxy resin as described below in addition to the alkali-soluble resin as described above. The epoxy resin is a compound having two or more epoxy rings such as a bisphenol A type, a cresol novolac type, a biphenyl type, or an alicyclic epoxy compound in a molecule. For example, bisphenol A type can be used: Epotohto YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-105 9, YDF-8170, YDF-170, etc. (The above is Dongdu Huacheng (share) system); DENACOL EX-1101, EX-1102, EX-1103, etc. (above is Changchun Chemical Industry Co., Ltd.); PRAXEL GL-6 Bu GL-62, G101, G102 ( The above is manufactured by Daicel Chemical Industry Co., Ltd., etc.; other bisphenol F type and bisphenol S type epoxy resins similar to these may be used. Further, an epoxy acrylate such as Ebecryl 3700, 370 1, 600 (above, Daicel-UCB Co., Ltd.) can also be used. The cresol novolac type may, for example, be Epotohto YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (the above is manufactured by Tohto Kasei Co., Ltd.); DENACOL EM-125, etc. Changchun Chemical Industry Co., Ltd.); biphenyl type can use 3,5,3,,5'-tetramethyl-4,4'-diglycidylbiphenyl; alicyclic epoxy compounds can be used CELLOXIDE 2021 ' 2081' 2083' 2085' EPOLEAD GT-3 01 ' GT-302, GT-401, GT-403, EHPE-3150 (above manufactured by Daicel Chemical Industry Co., Ltd.); SUNTOHTO ST-3000, ST-4000, ST -508 0, ST-5 1 00, etc. (above is Dongdu Huacheng (share) -53- 201205194); ugly? 1.1〇11 430, the same as 673, the same 695, the same 8508' with 40 32 (above is made by Dainippon Ink Chemical Industry Co., Ltd.). In addition, 'i,l,2,2-tetra(p-glycidoxyphenyl)-ethene, di(p-glycidoxyphenyl)decane, triglycidyl-monoglycidyl-(I) can also be used ( Ethyl ethyl ester, diglycidyl phthalate, bisglycidyl methacrylate, Epotohto YH-434, YH-434L·, an amine-type epoxy resin, bisphenol A type with dimer acid A glycidyl ester obtained by denaturation of an epoxy resin skeleton or the like. Among them, it is preferred that the molecular weight/epoxy ring is in an amount of 1 Torr or more, preferably 130 to 5 Å. When the amount of the molecular weight/epoxy ring is small, the hardenability is high and the shrinkage at the time of hardening is large. When the amount is too large, the hardenability is insufficient, which may result in a lack of reliability or flatness deterioration. Specific preferred compounds satisfying this condition may, for example, be Ep〇t〇ht〇YD-115, 118T, 127, YDF_17〇, YDpN 638, YDpN 7〇i, PRAXEL GL-61, GL-62, 3, 5, 3,5'-tetradecyl·4 4 ,-dihydrobiphenyl, CELLOXIDE 2021, 2081, EPOLEAD GT-302, GT-403, EHPE-3150, and the like. The amount of addition when epoxy resin is used as the (E) adhesive, and is hard in light: '! The total non-volatile content of the coloring composition is preferably in the range of 0.1% by mass to 3%, more preferably 0.5% by mass to 20% by mass, most preferably 1%, and 22: if the amount is added for this range This does not hinder the photopolymerization: the scoop obtains sufficient exposure sensitivity and at the same time has thermal polymerization property, and the liquid dryness can also maintain the storage stability of the photoresist. -54-201205194 &lt;Other Additives&gt; Further, in the photocurable coloring composition used in the present invention, various conventional additives may be used in addition to the above components. The additives are described below. (Interacting Agent) When the pigment concentration is increased, the rheological property of the coating liquid can be generally increased. Therefore, the photocurable coloring composition is applied or transferred onto the substrate to form a photocurable coloring composition layer (coloring layer coating film). After that, film thickness unevenness is less likely to occur. Further, in particular, when a photocurable coloring composition (4) (colored layer coating film) is formed by a slit coating method, it is important to form a coating liquid for forming a photocurable coloring composition layer before drying to form a uniform thickness. Coating film. Therefore, it is preferred to include a suitable surfactant in the photocurable coloring composition. The above surfactant may, for example, be a surfactant of the Japanese Patent Publication No. 2003 3 3 7424 ^ ^ &gt; a ^ ^ ^ ^ Π -1 3 3600 ^ ^ ^ ^. A surfactant for improving coatability is a nonionic surfactant, a fluorine-based surfactant, a polyoxyn surfactant, or the like. The nonionic surfactant is preferably, for example, a polyoxyethylene glycol polyoxypropylene glycol, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl aryl hydrazine, a polyethylene oxide alkyl vinegar, or a polyoxidation. Nonionic surfactants such as propylene alkyl ethers, polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. 1 Specifically, there are polyoxyalkylene monools such as polyoxyethylene glycol and polyoxypropylene glycol, polyoxyethylenes such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, and -55-201205194 polyoxyethylene oleyl ether. Alkyl ethers; polyoxyethylene sulphate basic base bond, polyoxyethylene sulphide, succinct chemistry, polyoxyethylene diphenyl phenyl phenyl ether, polyoxyethylene propylene polystyrene _, Polyoxyethylene sulfonyl aryl sulfonate such as polyoxyethylene sulfhydryl phenyl squara; polyoxyalkylene dialkyl vinegar such as polyoxyethylene dilaurate, polyoxyethylene distearate, sorbitol needle fatty acid s intended to be a nonionic surfactant such as polyoxylated sorbitan fatty acid. Specific examples of such are 'Adekapluronic, Adekanol, and Tetronic (above: ADEKA Co., Ltd.); EMULGEN, RHEODOL (above: Kao Corporation); ELEMINOL, NONIPOL, OCTAPOL, DODECAPOL· Department, NEWPOL (above is Sanyo Chemical Co., Ltd.); PAIONIN (above is manufactured by Takemoto Oil Co., Ltd.); NISS NONION (above is manufactured by Sakamoto Oil Co., Ltd.). These commercially available products can be suitably used. HLB value (hydrophilic-lipophilic balance value;

Hydrophile-Lipophile Balance number) is preferably from 8 to 20, more preferably from 10 to 17% of a surfactant, preferably having a fluorine-based base at least at any of the terminal, main chain and side chain or A compound of a fluoroalkyl group. Specific commercial products include, for example, MEGAFACF142D, the same F172, the same F173, the same F176, the same F177, the same F183, the same 780, the same 78 with the R3 0, the same R〇8 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.); FLORARDFC-135, with FC-170C, with FC-430, with FC-431 (manufactured by Sumitomo 3M Co., Ltd.); surFl〇N S-112, with S-113, with S-131, with S-141, same S-145, the same S-3 82, the same SC-101, the same -56-201205194 SC-102, the same SC-103, the same SC-104, the same SC-105, the same SC-106 (made by Asahi Glass Co., Ltd.) ; EFTOP EF351, the same 352, the same 801, the same 802 (made by JEMCO Inc.). The polyoxo-based surfactant can be exemplified by, for example, Toray Silicone DC3PA, the same DC7PA, the same SH11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH-190, the same SH-193, the same SZ-6032. Same as SF-8428, the same DC-57, the same DC-1 90 (above is made by Toray-Dow Corning Co., Ltd.); TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 (above, manufactured by Momentive Performance Materials Japan Co., Ltd.). The surfactant is preferably used in an amount of 5 parts by mass or less, more preferably 2 parts or less, based on 1 part by mass of the coating liquid for forming the photocurable coloring composition layer. When the amount of the surfactant exceeds 5 parts by mass, the surface of the coating is often roughened and the smoothness is easily deteriorated. _ The alkali solubility of the unhardened part, in order to achieve further k-direction photohardenability, and the development of the product, then the organic carboxylic acid can be added, the car-family has a molecular denier θ ^ A low molecular weight organic carboxylic acid of 1,000 or less. Specifically, it can be exemplified, for example, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, trimethyl ethane fluorene, hexanoic acid, diethyl acetic acid, heptanoic acid, octanoic acid, etc. One yuan of tannic acid. Lean 3 ^ long", acid, malonic acid, succinic acid, glutaric acid, hexanoic acid, pimelic acid, - octyl hydrazine, azelaic acid, azelaic acid, tridecane II Acid (Brazil diacid), Acacia 暴 丙 malonate, ethyl malonic acid, dimercaptomalonic acid, methyl succinic acid, tetrada * w thiosuccinic acid, citraconic acid and other aliphatic binary -57- 201205194 Carboxylic acid; aliphatic tricarboxylic acids such as 1,2,3-propanetricarboxylic acid, aconitic acid, and capric acid; benzoic acid, o-toluic acid, cumene, 2,3-dimethyl An aromatic monocarboxylic acid such as benzoic acid or 3,5-dimercaptobenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, and 1,2,4-benzenetricarboxylic acid (preferable tricarboxylic acid) , 1,3,5-benzenetricarboxylic acid (isophthalic acid), 1,2,3,5-benzenetetracarboxylic acid (p-tetracarboxylic acid), pyromic acid (pyromellitic acid), etc. Group polybasic acid"; phenylacetic acid, phenoxyacetic acid, helium oxygen Phenoxyacetic acid, hydrogen atoporic acid, hydrogen cinnamic acid, bitter almond acid (phenylglycolic acid), phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamic acid , other fatty acids such as coumaric acid and shape acid. (Alkoxydecane compound) From the viewpoint of improving the adhesion to the substrate in each of the curable compositions used in the present invention, an alkoxydecane compound can be used, and a sulphur coupling agent can be used. A decane coupling agent, preferably having an alkoxyalkyl group as a hydrolyzable group capable of forming a chemical bond with an inorganic material, more preferably acting on a bond with a resin or forming a bond to exhibit affinity The (meth) acrylonitrile group, the phenyl group, the fluorenyl group, and the epoxy decane are more preferably (meth) propylene decyl propyl dimethoxy decane. In the total solid content of the curable composition of the present invention, the amount of the decane coupling agent to be added is preferably from 2 to 5.0% by mass, more preferably from 5% to 5% by mass. (Co-sensitizer) The photocurable coloring composition used in the present invention preferably contains a co-sensitizer (C〇-sensitizer). At the date of this issue, the total sensitization i i advances the sensitivity of the sensitizing dye or the initiator: light ray or suppresses the inhibition of polymerization by oxygen. Guanlan-58- 201205194 Examples of such co-sensitizers can be exemplified by amines, for example, in Journal of 高分子f Polymer Society, No. 3, 173, published by MRSander et al. Pp. (1972), 曰本特公昭第44-20189, Japanese Patent Laid-Open No. 51-82102, 曰本特开昭第52-1 34692, and Japanese Laid-Open No. 59-1-3 Compounds described in Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Wait. Specifically, it may, for example, be triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-nonyldidecylphenylamine or p-nonylthiodidecylphenylamine. Other examples of the co-sensitizer may, for example, be sulfides, for example, disulfide compounds in JP-A-59-75. Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, β-mercaptophthalene, and the like can be exemplified. Further, other examples of the co-sensitizer include an amino acid compound (for example, fluorene-phenylglycine), and an organometallic compound (for example, tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-42965. And a sulfur compound (for example, trithiane) described in Japanese Patent Publication No. 55-34414, which is described in Japanese Patent Publication No. 55-34414, Japanese Patent Application Laid-Open No. Hei No. Hei. From the viewpoint of increasing the curing rate by the balance between the polymerization growth rate and the chain transfer, the content of the co-sensitizer is preferably 0 with respect to the total solid content of the curable composition. The range of 30% by mass, more preferably the range of 25% by mass, and more preferably the range of ~5 to 2% by mass - 59-201205194 (Polymerization inhibitor) In the present invention, the curable composition In the production or storage, in order to prevent unnecessary thermal polymerization of the polymerizable polymerizable compound, the thermal polymerization inhibitor is added. The thermal polymerization inhibitor used in the present invention may be exemplified by hydrogenquinone. , p-methoxy succinct, di-butyl-pair Cresol, gallicol, tertiary butyl catechol, benzoquinone, 4'4-thiobis(3_fluorenyl-6-tertiary butylphenol), 2,2, fluorenylene N-nitrosophenyl hydroxyamine oxime (III) phenoxazine, phenothiazine, etc. Relative photocurable coloring composition, thermal polymerization The amount of the inhibitor added is preferably 〇·〇丨% by mass to 5% by mass. Further, a higher fatty acid derivative such as rosin or decylamine may be added as needed to prevent polymerization inhibition by oxygen. Further, it may be limited to the surface of the photosensitive layer in a drying process after coating, and the addition of the higher fatty acid derivative S' is preferably from 0.5% by mass to 10% by mass based on the photocurable coloring composition. (Plasticizer) In the present invention, an inorganic filler or a plasticizer may be further added to improve the physical properties of the photocurable coloring composition. A plasticizer such as dioctyl phthalate or phthalic acid Double eleventh brewing, triethylene glycol dicaprylate, dinonyl glycol phthalate, acid xylene The ester, the dioctyl adipate, the diester of sebacate, and the triglyceride glycerol may be added to the total mass of the polymerizable compound and the resin, and may be added in an amount of 10% by mass or less. -60 - 201205194 Containing the above components The photocurable coloring composition of the present invention can be cured with high sensitivity by exposure to ultraviolet laser light, has excellent pattern formability, and has a good shape and visible light transmittance for the formed color pattern, and is suitable for forming a color filter. Coloring pattern for light sheet β &lt;Production method of color filter for liquid crystal display device&gt; The method for producing a photocurable coloring composition and a color filter of the present invention is suitable for a color filter for a liquid crystal display device. Hereinafter, the photocurable coloring composition of the present invention and the method for producing the color filter will be described, but the present invention is not limited to this method. The color filter is produced by forming a photocurable coloring composition on a light-transmitting substrate to form a colored pattern. However, other steps may be further provided as needed. A method of producing a color filter according to the present invention includes a step of forming a colored layer, wherein the color filter composition of the present invention is provided on a substrate with a photocurable coloring composition to form a coloring composition. a coloring layer; an exposure step of exposing the colored layer to a pattern; and a developing step of developing the exposed coloring layer to form a colored pattern. Further, a step of baking the coloring layer (pre-bake step), and a step of co-coasting the developed colored layer (baking step) may be further provided as needed. Sometimes these steps are combined to be referred to as a pattern forming step. [Colored layer forming step] In the coloring layer forming step in the present invention, the photocurable coloring composition of the present invention is applied onto a substrate to form a colored layer. The substrate may, for example, be a non-glass for use in a liquid crystal display device, soda glass (soda -61-201205194 glass), borosilicate glass, quartz glass, or a transparent conductive film attached to such a glass, or a solid image. A photoelectric conversion element substrate used for a detector or the like. Further, a plastic substrate can be used. These substrates are preferably used to form a black matrix ' such as a lattice shape, and a colored pattern is formed on an empty portion of the lattice. An undercoat layer may be provided on these substrates as needed to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate. From the viewpoint of further exerting the effects of the present invention, the substrate is preferably large (about 1 m or more on one side). As a method of forming a colored layer on a substrate, various methods such as slit coating nozzle ink method, spin coating, cast coating, roll coating, screen printing method, and the like can be applied. Among them, slit coating is preferred from the viewpoint of precision and speed. Further, a method of transferring a coating film formed in advance to the temporary branch body by the above-described providing method to the substrate can be applied. Regarding the transfer method, the paragraph number [0023], [〇〇36]~[〇〇51], or 曰本特开2006-47592 of JP-A-2006-23696 can also be preferably used in the present invention. The production method described in the paragraph [0096] to [〇1〇8] of the Gazette. Regarding the layer thickness (for example, coating thickness) of the coloring layer in the present invention, in order to obtain a sufficient color reproduction region and obtain sufficient panel luminance, the film thickness after drying is preferably formed as 〇.5μιη~3.〇μηι More preferably, it is formed into 1.5 μιη~2.5 μιη. Further, when a coloring layer composed of a photocurable coloring composition having a film thickness of 2 μm after drying is formed, the colored layer is at a wavelength of 355 〇 when the tooth permeability of -62 to 201205194 is 2% or less. A preferred embodiment of the effect of the present invention is exhibited satisfactorily. That is, the exposure light source length used in the exposure step described later is usually in the range of 300 nm to 380 nm, but the photocurable composition of the present invention is irradiated with an exposure light source having such a wavelength, and the pattern shape is good at the time of formation, and remains. The occurrence of the object is small, the property is also excellent, and excessive movement does not occur in the post-baking step, so that the shape of the pattern after development can be maintained, and in particular, the effect of preventing cracking of the contact hole can be exhibited. [Exposure Step] The exposure step in the present invention forms a latent image by exposing the colored layer using a laser beam of the image or by irradiating it with a mask having a pattern. It is considered that the exposure step of the invention can be carried out in the exposed region of the photocurable coloring composition by the generation of the (c) photopolymerization initiator, and the (D) polymerizable compound can be produced. In the polymerization hardening reaction, a hardening reaction is caused by heat generated by exposure to ultraviolet light, and the exposed region is subjected to light/heat double hardening to form a pattern composed of a hardened region and an uncured region. One of the characteristics of the ultraviolet laser used in the present invention is high, and in the exposure step, heat is sometimes generated in the photocurable coloring composition, so that hardening unevenness occurs inside the formed halogen. Since it is controlled to control the temperature of the exposed object (the temperature of the photohardenable coloring sheet), it is preferable to keep the temperature of the exposure stage constant, and it is also necessary to consider the rise of the light table. In addition, the ultraviolet light is laser-lighted. The parallelism is preferably high because it is less affected by the distance from the substrate, and the substrate is floated and transported by air while being exposed. The wave is colored in the image development heat flow, and the outer line of the pattern is over the original pattern. In the case of the illuminance of the medium, I)) to the exposure of this -63- 201205194 laser excitation medium is crystal, glass, liquid, pigment, gas, etc. 'Solid solid laser, liquid thunder using these media A laser having a radiation wavelength (oscillation wavelength) among conventional ultraviolet light such as a shot, a gas laser, or a semiconductor laser. Among them, from the viewpoint of the output of the laser and the wavelength of the radiation, a solid laser or a gas laser is preferable. The exposure wavelength of the ultraviolet laser used in the present invention is preferably in the range of 300 nm to 380 nm, more preferably 31 〇 nm to 36 Å, in view of the fact that the photosensitive wavelength of the photosensitive resin composition is uniform and the sensitivity is good. The range of nm is particularly good for laser exposure at 355 nm wavelength. Specifically, it is preferable to use a third wave (355 nm) of a Nd·YAG laser which outputs a large and inexpensive solid laser, or XeCl (308 nm) and XeF (3 53 nm) of a pseudo-molecular laser. Further, the exposure amount of the object to be exposed (pattern) is, for example, in the range of lmJ/cm2 to l〇〇mj/cm2, preferably in the range of imj/cW to 5〇mJ/cm2. If the amount of exposure is this range, it is preferable in terms of productivity in pattern formation. The ultraviolet laser used in the present invention is preferably a pulsed laser that emits (oscillates) at a frequency of 20 Hz to 20 Hz from the viewpoint of productivity. The exposure apparatus to be used in the present invention is not particularly limited, and the commercially available product may be EGIS (manufactured by V-TECHNOLOGY Co., Ltd.) or DF2200G (manufactured by DAINIPPON SCREEN Co., Ltd.). Devices other than the above are also applicable. Further, it is also preferable to use an actinic radiation (a c t i n i c r a d i a t i ο η ) having a wavelength of 300 nm or more and 450 nm or less. When exposure is performed by actinic radiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, or the like can be used. -64- 201205194 S When using a mercury lamp, it is preferable to use actinic radiation having wavelengths of g line (4 3 6 n m ), i line (365 nm), and 11 line (405 nm). [Developing Step] The developing step in the present invention develops a coloring layer on which the above-described latent image is formed to form a pattern. The exposed region is hardened into a pattern, and subjected to an in-situ development treatment in the development process, so that the unirradiated portion (unhardened portion) in the above exposure step is dissolved in the alkaline aqueous solution and then removed, and only the photohardened portion remains. Thus, a pattern can be formed. The developer is an organic alkali developer or an inorganic alkali developer, or a mixture thereof. The alkali agent used in the developer may, for example, be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine or dimethanolamine. Organic basic compound such as tetramethylamine hydroxide, tetraethylamine hydroxide, cholin, pyrrole, piperidine, l,8-diazabicyclo-[5 _4.0]-7-undecene It is preferable to dilute such an alkaline compound with pure water to an aqueous solution having a concentration of 〇〇〇1 to 1% by mass, preferably OOiq mass/〇, as a developing solution. Further, when a developer containing such an aqueous solution is used, it is usually washed with pure water (water wash, r i n s e ) after development. The developing temperature is preferably 2 (rc~35t:, more preferably 23t~3 (rc^ development time is preferably 30 seconds to 12 seconds, more preferably 4 seconds to 9 seconds). A preferred combination with the development time is, for example, a temperature of 25. The temperature is 50 seconds to 100 seconds, and the temperature is 3 seconds to 40 seconds to 8 seconds. Further, the spray pressure is preferably 〇1 MPa to 0.5 MPa. (^^^~(^^^, and "(10)^(10)^ By selecting these conditions, the shape of the pattern can be arbitrarily designed into a rectangular shape or a tapered shape. -65- 201205194 [Baking Step] The present invention In order to make the photocurable, 丨π® must be hardened, the target is hardened.

In addition to the § and the development of the aforementioned thinking, do, and J. The method of baking can be carried out by the pair and the ancient part is, # , . + a 8 The pattern of the developed and washed pattern uses a heating plate or a convection oven (埶M ppm, base ots J. ^ -u, hot air) Heating means such as a % dryer and an ancient frequency heating machine are carried out continuously. Type or batch type heating As the condition for baking, the temperature is preferably isn°r~. 马£马150 c~260 c, more preferably 260C ‘best 9〇f)°r Ovirv. Gossip is C. The baking time is preferably 10 knives, 4 liters, 1 5 〇 minutes, and more preferably 2 〇 8 〜 9 〇 minutes. &amp; good for 2 knives clock ~ &quot; Ο minutes, the best is 2 〇 minutes In addition, the color pattern: into, exposure, layer formation, baking. Therefore, the color filter forms an RGB three-color layer, a light-shielding layer, or the like, and a plurality of hue can repeat the cycle of the colored layer and the baking cycle of the desired color, and the color can be colored and exposed for each hue. After development, the final color is dried together with all the hue to produce a coloring element containing the desired hue. [Other steps] No 'fabric', "Ming, ^ ^. + Ma is formed by coating or the like before the exposure step. The color layer is dry, and the step of pre-baking can also be provided. The pre-bake of the colored layer is preferably 6〇eC~14 (TC' is better than 8 (TC~120°c. Pre-person) Smart time

Cce a s live for 30 seconds to 300 seconds' more preferably 80 seconds to 200 seconds. &lt;Liquid day display device ^ The present invention is extravagant, *U shi shi zhen / Ba Yingguang film is suitable for the production of liquid crystal display device 'making π Μ + invention map / dry station ¥ ^ 莱 形成The liquid crystal display of the filter 201205194 The definition of the display device or the description of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association (share), issued in 1990)", "Display device (Ibuki Shunzhang) , the industry book (shares) 'Ping Cheng first year issued" and so on. In addition, the liquid crystal display system has been described in, for example, "Next Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Research Association, Ltd., issued in 1994)" There is no particular limitation on the liquid crystal display device to which the present invention can be applied. The present invention can be applied to, for example, various types of liquid crystal display devices described in the "next generation liquid crystal display technology". The color light-emitting sheet of the present invention is particularly effective for a color TFT type liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display device (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention is also applicable to a liquid crystal display device such as a horizontal electric field drive method such as IPS, a pixel division method such as MVA, or the like, or STN, TN, VA, OCS, FFS, and R-OCB. Further, the color filter of the present invention is also preferably provided in a bright and high-precision C〇A (C〇l〇r-filter 0n Array) method. In the case of the c〇A type liquid crystal display device, in addition to the above-mentioned general requirements, the required characteristics of the color filter layer are required to have the required characteristics of the interlayer insulating film, that is, low permittivity and peeling liquid resistance. . In addition to the exposure method by the ultraviolet laser, the color filter or the film thickness of the halogen specified by the present invention is selected, and it is considered that the ultraviolet laser as the exposure light source can be improved. Penetration. Thereby, it is possible to form a pixel in which the coloring property of the coloring pigment is improved and there is no defect or peeling or squeaking, so that it is possible to improve the coloring layer directly or indirectly provided on the TFT substrate, in particular, the improvement of the peeling liquid resistance. The liquid crystal display device of the c〇A type is set to -67-201205194. It is also possible to provide a resin film on the color filter layer in order to satisfy the required characteristics of the full low valley rate. In order to advance the ITO electrode on the color layer and the end of the driving substrate below the coloring layer, it is necessary to form a rectangle having a side length of about 1 to 4 〇μΐΏ on the coloring layer formed by the c〇A method. Or a circular or elliptical 々β " „ , , 憜 _ shape, or "〕" shape with a diameter of 1 to 40 μπιΦ. The cross-sectional shape of the pixel is a rectangular to conical anchor hole (guide path), especially It is preferable to make the size of the conduction path (i.e., the side length) 5 μm or less, but it is also possible to form the channel of s, s, and v of 5 μm or less by using the present invention. When the cross-sectional shape of the contact hole does not have a rectangular to a conical shape, ^ or is not sufficiently opened, the disconnection or the conduction of the transparent conductive film may occur, and such a defect occurs. When the color filter is used for the image display device, the coloring composition can be used to display the problem. Due to the deterioration of the shape of the contact hole and the rupture, the backlight is printed on the backlight ##N (A ν 咕° is contained in SID meeting Digest 1380 (2005)l A.Konno et al.), or the monthly publication DISPLAY, 2005 The 18th to 24th pages (Island Kangyu) 200 The 5th December issue will be made by the invention of the Figure 3 (Page 8). The liquid crystal display device and the color filter produced by the fish formation method can be used for high contrast at the same time. The three-wavelength tube group RGB-LED of the conventional cold cathode tube is used as the back; the red, green and blue LED light source (ϋ P # if Μ ^ ♦ source) can provide high brightness and high color purity. [Liquid Embodiment] The present invention will be described more specifically with reference to the accompanying drawings, but the present invention is not limited to the following examples. In addition, otherwise "parts" and "%" are the quality standards. -68- 201205194 - Synthesis of a polymer compound having a hetero ring in a side chain - (synthesis of polymer 1) M-6 (structure described below) 27.0 g 126.0 g of methyl methacrylate, 27.0 g of methacrylic acid, and 0.00.0 g of 1-decyloxy-2-propanol were introduced into a three-necked flask substituted with nitrogen to a stirrer (Xindong Science Co., Ltd.: THREE- ONE MOTOR) is stirred and heated while flowing nitrogen into the flask to a temperature of 90 ° C. 2,2-azobis(2,4-dimercaptophthalonitrile) (Wako Pure Chemicals Co., Ltd.) was added thereto. V-65) 1.80g, heated and stirred at 90 ° C for 2 hours. After 2 hours, add 1.8 0 g of V-65 and After hot stirring for 3 hours, a 30% by mass solution of the polymer 1 was obtained. The weight average molecular weight of the obtained polymer 1 was measured by a gel permeation chromatography (GPC) using polystyrene as a standard to be 21,000. Further, by titration with sodium hydroxide, the acid value per solid component was 99 mgKOH/g. M-6 -69- 201205194 (Production of coated pigment 1) Pigment (CI $目At 丄颜枓Blue 15 : 6) 50g, sodium chloride 500g, solution of the above polymer 1 2 〇pfen _ g and 100g of monoethylene glycol are added to a stainless steel 1 gallon kneading machine (in the well, 激ί· system, t ash The mixture is kneaded for 9 hours. Secondly, the material force is from about 3 liters of water to about 3 liters of water. After mixing for about 1 hour with a high speed mixer, it is filtered, washed with water to remove sodium vapor and solvent, and then dried. The coating pigment 1 is prepared. (Preparation of the coating pigment 2) ^ The same as the above, except that the pigment (CI pigment blue 15.6) used in the preparation of the breaker pigment 1 is changed to a pigment (CI·Pigment Violet 23) Way to modulate the coated pigment 2. - Photocurable coloring composition layer forming step _ (Pigmentation Preparation of Composition 1 The pigment dispersion composition 1 was prepared as follows. That is, 'the composition described below was stirred for 3 hours at a number of revolutions of 3,00 Or. pm using a homogenizer and mixed to prepare a mixed solution, and further 0.1 was used. The bead disperser of the mmtp zirconia beads, ULTRA APEX MILL (manufactured by Shou Industrial Co., Ltd.), was subjected to dispersion treatment for 8 hours. Further, the organic solvent propylene glycol oxime ether acetate was described as PGMEA. • Coated pigment 1 16.5% Dispersant: Disperbykl61 BYK company [30% solution] 8% • Alkali-soluble resin: phenyl decyl acrylate / methacrylic acid = 75/25 [mass ratio] Copolymer (weight flat solid Ingredient 50%)) PGMEA solution with a molecular weight Mw of 5000% 2% 7 3.5%

PGMEA-70-201205194 (Preparation of Pigment Dispersion Composition 2) The pigment dispersion composition 2 was prepared by the same operation as the preparation of the pigment dispersion composition 1 by the composition described below. • Coated pigment 1 11.55% • Coated pigment 2 4.95% • Dispersant: Disperbykl61, BYK company [30% solution] 8% • Alkali-soluble resin: benzyl methacrylate / methacrylic acid = 75/25 [mass ratio Copolymer (PGMEA solution (solid content: 50%) having a weight average molecular weight Mw of 5000) 2% _ PGMEA 73.5% &lt;Example 1 &gt; (Preparation of photocurable coloring composition) Stirring and mixing the composition shown below The composition of 1 modulates a blue photocurable coloring composition. • Pigment Dispersion Composition 1 9.08 parts • Pigment Dispersion Composition 2 5.59 parts • Surfactant: F-554 0.2% PGMAI solution manufactured by DIC Corporation 5.0 0 parts • Decane coupling agent (structure described below) 0.20 parts • Photopolymerization start Agent (structure described below) 0.6 8 parts • Polymerizable compound (type and amount of the compound described in Table 1) • Adhesive: allyl methacrylate/mercaptopropionic acid = 80/20 mol% copolymer weight average Molecular weight 30000 20% PGMEA solution 18.54 parts • Solvent: PGMEA 8.72 parts -7 1- 201205194 i (0C Η3&gt;3 Ο 矽 偶 coupling agent

Polymerization initiator (formation of photocurable coloring composition layer) The obtained blue photocurable coloring composition was applied to a glass substrate by slit coating. Specifically, the interval between the slit and the glass substrate and the amount of discharge were adjusted so that the layer thickness of the photocurable coloring composition layer after post-baking was 32 μm, and the coating was applied at a coating speed of 120 mm/sec. - prebaking step, exposure step - second 'heating at 1 〇〇 °c using a hot plate (prebaking treatment) 120 seconds later, using Nd : YAG laser (Pulseo, third wave 355 nm, The exposure apparatus of Spectra-Physics Co., Ltd. adjusts an optical system so that the irradiation energy of the surface of the photo-curable coloring composition layer is about 1.0 mJ/cm<2> and is exposed by the reticle (mask diameter 25 [mu]m). -72- 201205194 Multiple exposures were performed on the surface of the photocurable coloring composition layer for pattern exposure. -Developing step, post-baking step - Subsequent 'Using a developing device (manufactured by Hitachi High-technologies Co., Ltd.) to develop a solution of potassium hydroxide-based developing solution CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) The liquid obtained by diluting the aliquot of CDK-1 with 99 parts of pure water) set the spray pressure to 0.2 MPa, and the time during which the unexposed photocurable coloring composition layer is dissolved to expose the glass surface plus 2 sec. The time was developed and washed with pure water. Next, post-baking treatment was carried out in a clean oven of 220 ° C for 3 minutes, that is, a substrate having a blue halogen containing heat-treated finish was formed. The following evaluations were carried out and the results are shown in Table 2. (Evaluation) [Residual opening ratio of contact hole opening diameter and post-baking] A circular pattern for forming a contact hole (hereinafter sometimes referred to as 、φ) having a halogen content of 25 μΓηφ (mask diameter 25^) The mask of φ), the second exposure GAP = 150_ the colorant for color filters was formed in the above step, and the CH opening diameter after the post-baking step was measured. Further, the CH residual σ diameter and the opening diameter after the post-baking step were used to calculate the CH residual ratio by the following formula. η Responsibility rate (/.) = post opening diameter (after post-baking) clearance (before post-baking)] χ1〇〇-73- 201205194 [developability] For the above coating step, photocurable coloring Development is carried out under the conditions of the composition layer, and it is measured that the composition layer is dissolved to expose the glass surface to be smaller. [Line Width Sensitivity] The higher the development width of the glass substrate cover 'on which is subjected to the above-described coating step and the coloring composition layer, under the condition of the development step of the above-mentioned exposure step, the higher the sensitivity. [Residue] A halogen periher electron microscope (SEM) of a glass substrate used for the aforementioned line width sensitivity layer was evaluated. - Evaluation criteria - time (seconds) from the pre-baking step and the exposure step to the photo-curable coloring of the unexposed portion of the development step. The number-recovery pre-baking step is accompanied by photocurability ‘substance exposure through a mask line width of 17 μm η, and the line width of the halogen formed later is measured. The glass surface of the edge portion of the photo-curable coloring group is attached by scanning, and the residue is observed according to the following reference: 0: Residue is generated. χ : No residue is produced. &lt;Examples 2 to 8, Comparative Example 1 to Team Holes, and the preparation of the photocurable coloring composition are described in Table 1 : In the same manner as in Example 1, a blue lanthanum was formed and implemented. example! In the same way, the CH opening diameter, ": ' is evaluated by the line width sensitivity and the residue. The result is encapsulated and shown in the following, -74-201205194 [Table i] Polymerizable compound specific polymerizable compound DPHA Type usage (parts) Usage (parts) Example 1 1 1.09 1.09 Example 2 2 1.09 1.09 Example 3 3 1.09 1.09 Example 4 4 1.09 1.09 Example 5 5 1.09 1.09 Example 6 6 1.09 1.09 Example 7 1 2.19 - Example 8 5 2.19 - Comparative Example 1 - - 2.09 Comparative Example 2 Comparative Compound 1 1.09 1.09 Comparative Example 3 Comparative Compound 2 1.09 1.09 The specific polymerizable compounds 1 to 6 used in Table 1 are shown below. Further, DPHA is dipentaerythritol hexaacrylate (trade name: DPHA) manufactured by Sakamoto Chemical Co., Ltd., and corresponds to the polymerizable compound (III) of the present invention. Further, Examples 1 to 6 In the comparative examples 2 to 3, two types of polymerizable compounds were used. Specific polymerizable compound 1 · Nagase Chemical name product, DA-722, manufactured by ChemteX Co., Ltd. Specific polymerizable compound 2: Trade name EA-5420, manufactured by Shin-Nakamura Chemical Co., Ltd. Sex Compound 3: Product name: EA-5421, manufactured by Shin-Nakamura Chemical Co., Ltd. Product name: EA-5323, manufactured by Shin-Nakamura Chemical Co., Ltd. Specific polymerizable compound 5: EA-5324, manufactured by Shin-Nakamura Chemical Co., Ltd. Polymeric Compound 6: Manufactured by Shin-Nakamura Chemical Co., Ltd., EA-5721-75-201205194 Further, Comparative Compound 1 used in Comparative Example 2 is a polymerizable compound having an aromatic ring, that is, "Naka Nakamura Chemical" having the following structure The industrial name of the company is EA-6320. Further, the comparative compound 2 used in Comparative Example 3 is a polymerizable compound having an OH group other than glycidol, that is, the product name "Alisons M-305" manufactured by Toago Seisakusho Co., Ltd. having the following structure.

Comparative Compound 1 Comparative Compound 2 &gt; -76 201205194 [Table 2] Contact hole developability (sec) Line width sensitivity (μιη) Residue opening diameter (μπ〇 residual ratio (%) Example 1 23.5 92 72 171.4 〇Example 2 23.2 98 75 171.3 〇 Example 3 19.4 75 64 171.1 〇 Example 4 18.4 72 61 171.5 〇 Example 5 26.3 105 82 171.5 〇 Example 6 14.7 55 62 171.5 〇 Example 7 24.0 101 68 169.5 〇 Example 8 26.6 111 91 168.1 〇Comparative Example 1 3.5 15 97 171.2 X Comparative Example 2 11.7 46 220 168.5 X Comparative Example 3 2.5 10 70 171.0 〇 From the results of Table 2, the color filter of the example (having the photocurable coloration by the present invention) The colored color filter of the coloring matter obtained by the composition has a large CH opening diameter and a good CH residual ratio. Thus, it is understood that the colored pattern formed by the photocurable coloring composition of the present invention can be appropriately suppressed by the post-baking station. The induced thermal deformation and the cracking of the contact hole caused by the heat treatment are suppressed. It is also known that the developability of the embodiment is good, and the line width sensitivity of the embodiment is equivalent to the comparative example, and the residual of the embodiment As described above, it is understood that the photocurable coloring composition of the present invention is superior to the conventional one in the use of the colored pattern of the color light-passing sheet, particularly It is more excellent in the formation of contact holes. [Simplified description of the drawing] 益〇 [Main component symbol description] jitfi 〇-77-

Claims (1)

201205194 VII. Patent Application Range: 1 · A photocurable coloring composition for color filters containing (A) an organic solvent, (B) a pigment, (C) a photopolymerization initiator, and (D) a polymerizable compound And (E) an adhesive agent, wherein the (D) polymerizable compound contains one or more compounds selected from the group consisting of the following (I) and (II), and (I): two or more and six or less (fluorenyl) groups. a polymerizable compound having a propylene group, one or more and six or less hydroxyl groups derived from a glycidyl group, and a ring structure other than an aromatic ring; (II): having three or more (12-hydroxy) fluorenyl groups A polymerizable compound derived from one or more of 12 or less hydroxyl groups and a branched structure of a glycidyl group. 2. The photocurable coloring composition for a color filter according to the first aspect of the invention, wherein the ring structure other than the aromatic ring in the above (I) is selected from the group consisting of a hexahydrophthalic acid skeleton and tetrahydrogen. One of a group of an phthalic acid skeleton, a hydrogenated bisphenol A skeleton, a cyclohexanediketanol skeleton, an iso-cyanuric acid ring, and a tricyclodecane dimethanol skeleton. 3. The photocurable coloring composition for a color filter according to the first aspect of the invention, wherein the branched structure in the above (II) is selected from the group consisting of a trihydrocarbyl propane skeleton, a neopentyl alcohol skeleton, and two One of a group of a pentaerythritol skeleton, a sorbitol skeleton, and a glycerin skeleton. 4. The photocurable coloring composition for a color filter according to the first aspect of the invention, wherein the (D) polymerizable compound further contains (III) (meth)acrylic fluorenyl group having three or more and 12 or less The number of (meth)acryl fluorenyl groups divided by the molecular weight of the polymerizable compound is from 0.0067 to 0.0114 or less, and a polymerizable compound having a structure different from the above (I) and (II) is contained. -78-201205194 5. The photocurable coloring composition for a color filter according to the invention of claim i, wherein the film thickness after drying using the photocurable coloring composition of the color filter is When the coloring layer of 2 μm is used, the transmittance of the colored layer at a wavelength of 355 nm is 2% or less. 6. The photo-curable coloring composition of the color filter of claim 1 wherein the (B) pigment is C.I. Pigment Blue 15:6. 7. A method of producing a color filter, comprising: a coloring layer forming step of providing a color filter for a color filter according to any one of claims 1 to 6 to a substrate Forming a coloring layer containing the colored composition; exposing the colored layer to a pattern; and developing a step of developing the exposed colored layer to form a colored pattern. 8. The method of producing a color filter according to claim 7, wherein the exposing step is an exposure step of exposing to a pattern using a laser of 355 nm. 9. The method of manufacturing a color filter according to the seventh aspect of the invention, which is a method of manufacturing a color filter in which a color light-emitting sheet is placed on an array substrate (C〇i〇r_fiiter 〇n Array). 1A, a color filter manufactured by the method of producing a color filter according to claim 7 of the patent application. A liquid crystal display device comprising the color filter of the first aspect of the patent application. -79- 201205194 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: