TW200902579A - Colored photosensitive composition - Google Patents

Abstract

The present invention provides a colored photosensitive composition having sufficient sensitivity, good adhesion in linearity and forming a pattern excellent in contour and shape. The colored photosensitivity composition comprises a photopolymerizable material (A); a photopolymerizable initiator (B); and a colorant (C), wherein the photopolymerizable compound (A) comprises a resin (A1) obtained by reacting a reaction product of an epoxy compound (a-1) and an ethylenic unsaturated group-containing carboxylic acid compound (a-2) with a polybasic acid anhydride (a-3), and the A1 comprises the unit derived from the epoxy compound having the biphenyl group framework and the unit derived from the epoxy compound having the cardo framework.

Description

200902579 IX. Description of the Invention: [Technical Field] The present invention relates to a color-sensitive photosensitive composition, and more particularly to a color-sensitive photosensitive composition which can be used for forming a light-shielding film which is used for color filter Among the black matrix of the piece, etc. [Prior Art] Conventionally, as a method of producing a color filter using a pigment, a dyeing method, an electrodeposition method, an inkjet method, a pigment dispersion method, and the like have been known. In the case of the pigment dispersion method, a photosensitive resin obtained by dispersing a pigment by a dispersant or the like is added with a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc., to obtain a photosensitive coloring. The resin composition is applied onto a glass substrate, dried, and then exposed and developed to form a color pattern. Thereafter, heating is performed to fix the pattern to form a pixel. These steps are repeated for the colors to form a color filter. The photosensitive coloring grease composition for forming an image of such a color filter is required to have sufficient analytical properties and adhesion to a substrate and a small amount of development residue. Moreover, in the case of the pigment dispersion method, it is required to supply to the photolithography step, so the industry has been striving that no residue or segregation is generated in the removed portion of the development step; the removed portion has sufficient solubility; (edge) clarity and other pixel formation. Further, in recent years, as the size of the substrate to be used has increased, the development of the margin has been demanded. In particular, as in the case of black matrices, it is required to cover the whole wavelength region of light. It is known that the branching is perforated, and each tree is dissolved into the light.

In the case of 200902579, it is very difficult to set the difference in crosslink density between the exposed portion and the unexposed portion. Therefore, even in the exposed portion, the side of the light-emitting surface is sufficiently hardened, but it is not cured on the side of the base surface. Further, since a large amount of black coloring material which is insoluble in the developer is blended, there is a problem that developability is remarkably lowered. Therefore, in order to solve such a problem, a photosensitive colored resin composition having a novolac epoxy acrylate as a binder has been disclosed (for example, refer to Patent Document 1 and discloses the use of a carboxyl group. A reaction product of an acrylic resin and an aliphatic epoxy group-containing unsaturated compound is used as a binder resin composition (for example, see Patent Document 2). Further, it is disclosed that an acid anhydride is contained and two epoxy groups are contained. A resin composition of a polyvalent carboxylic acid obtained by reacting a compound with a reaction product of a monocarboxylic acid (see Patent Document 3). [Patent Document 1] Japanese Patent Laid-Open Publication No. U-84 No. 1-26 [Patent Document 2] Japanese Patent [Patent Document 3] Japanese Patent Laid-Open Publication No. JP-A No. WO 04-43 The composition of the resin disclosed in the above is insufficient in sensitivity, poor in fine line adhesion, easy to peel off, and residual residue, etc. Moreover, since the development margin is small, there is a shadow and peeling off. To the exposure part, the edge of the pattern is not flat, etc. The problem arises between the two, so the carboxyl group tree). The present invention is based on the above-mentioned problems, and aims to provide a color-sensitive photosensitive composition which has sufficient sensitivity and good fineness and can be used. A pattern having an excellent contour shape is formed. [Means for Solving the Problem] The present inventors have found that the present invention has been accomplished by solving the above problems in order to solve the above problems, and the present invention has been completed by the following coloring photosensitive composition, and the colored photosensitive composition is contained therein. A resin (A1) obtained by reacting a specific compound epoxy compound (a-1) with a reaction product containing an ethylenically unsaturated acid compound (a-2) and further with a polybasic acid anhydride (a-3). More specifically, the present invention provides a coloring photosensitive composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a component (C), characterized in that the photopolymerizable compound (A) a resin (A1) obtained by reacting an epoxy compound (a-1) with a carboxylated (a-2) group containing an ethylenically unsaturated group, and further reacting with a polybasic acid anhydride (a-3); The above (a-1) contains a compound having a biphenyl skeleton and an epoxy compound having a leaf D (C ard 〇) skeleton. [Efficacy] According to the present invention, by blending resins having different skeletons, it is possible to form a pattern excellent in linearity with sensitivity. Further, it is possible to easily form a fine line-free peeling or residue on the sheet, and an undercut shape is formed during development, and a good black matrix pattern excellent in contour shape is used for the wiring. The problem is that the carboxylic acid is carried out, and the coloring is compounded to obtain a non-destructive epoxy substrate. 200902579 Since the undercut shape is not formed during development, it is easy to provide a color filter for liquid crystal displays with good fineness of 1 ο # m or less, high contrast, and excellent color rendering of R, G, and 液晶. Light film. Further, when the concentration of the color material is high, a photosensitive coloring resin composition for a color filter excellent in image formation property, a color filter using the photosensitive colored resin composition, and a liquid crystal display device can be provided. . Further, by combining a specific binder resin and a dispersing agent, it is possible to provide a photosensitive colored resin composition for a color light-passing sheet which is excellent in balance between sensitivity and solubility and which is excellent in sharpness and adhesion of pixel edges. . [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. The colored photosensitive composition of the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), and a color former (C). <Photopolymerizable Compound (A) > The photopolymerizable compound (A) is a substance which is polymerized by irradiation with light such as ultraviolet rays to be cured. Specifically, the photopolymerizable compound (A) contains a reaction product of an epoxy compound (a-fluorene) and an ethylenically unsaturated group-containing carboxylic acid compound (a-2) and a polybasic acid anhydride (a-3). The resin (A1) obtained by carrying out the reaction. Further, the epoxy compound (a-fluorene) contains an epoxy compound having a biphenyl skeleton and an epoxy compound having a Car do skeleton. The above resin (A1) can be used in the following two aspects. In the first aspect, the resin (A1) contains: by reacting the epoxy compound having the biphenyl bone 8 200902579 frame with the component (a-2) as the (a-1) component, a resin (A 1 -1 ) obtained by reacting a component; and by reacting the (a - 3 ) component as an (epoxy compound having an anthracene skeleton and a component (a-2) as a component Resin obtained by the reaction (In other words, the resin (A 1 ) contains a resin (A 1 ) and a resin (A 1 - 2 resin mixture, the resin (A 1 -1 ) contains a compound having a biphenyl skeleton oxygen compound) a unit derived therefrom, and the resin (A 1 - 2 ) contains a unit derived from an epoxy compound having a skeleton. Further, in the second aspect, the resin (A1 ) contains: by making (a-Ι) a resin having a biphenyl skeleton and a reaction product of a ruthenium epoxy compound and a component (a-2), and further a resin obtained by reacting a component (Ab 3 ). In other words, a resin Containing a resin (A 1 - 3 ) containing the epoxy compound having a biphenyl group a unit, and a unit derived from a cyclone having a skeleton of 0f °. The unit derived from the above epoxy compound (a-1) having a biphenyl skeleton, and derived from an epoxy compound having 0 skeleton The unit amount is preferably 1:99 to 80:20, more preferably 5:95 to 30: by having an epoxy compound (a-1) having a biphenyl skeleton derived from The mass of the unit derived from the epoxy compound of the skeleton is within this range, and the linearity of the pattern and the contour after development can be made good. [Epoxy compound (a-1)] The epoxy compound used in the present invention (a -1 ) has a biphenyl-3) a -1 ) reaction 2) °) The ring has yttrium as the tibia-3) (A1) The skeleton is oxidized to produce 70 ° tto Bone 9 200902579 Epoxy compound and epoxy compound with anthracene skeleton. [Epoxy compound having a biphenyl skeleton] An epoxy compound having a biphenyl skeleton, having one or more biphenyl skeletons represented by the following chemical formula (4) in the main chain, and having one or more rings Oxygen. The epoxy compound (a-1) is preferably one having two or more epoxy groups, and the epoxy compound (a-1) may be used singly or in combination of two or more. [Chemical 1]

In the formula (4), a plurality of R1's are each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an i atom or a phenyl group which may have a substituent, and 1 represents an integer of 1 to 4. Among the epoxy compounds having a biphenyl skeleton, an epoxy compound represented by the following formula (1) is preferably used, and an epoxy compound represented by the following formula (2) is particularly preferably used. By using the epoxy compound of the formula (2), it is possible to provide a color-sensitive photosensitive composition which is excellent in balance between sensitivity and solubility, and which is excellent in clarity and adhesion of the pixel edge. [Chemical 2]

[In the formula (1), a plurality of R1 are each independently, and represent a hydrogen atom, carbon 10 (1) 200902579, an alkyl group of 1 to 12, an i atom, or a stupid group which may have a substituent, and η represents a 1-4. Integer. m is an average value and represents a number from 0 to 10, preferably less than one. 〕 [Chemical 3]

[In the formula (2), m is an average value, and represents a number of 0 to 10, preferably less than 1. Further, among the epoxy compounds having a biphenyl skeleton, an epoxy compound represented by the following formula (5) is preferably used. By using the epoxy compound of the formula (5), it is possible to provide a color-sensitive photosensitive composition which is excellent in balance between sensitivity and solubility, and which is excellent in sharpness and adhesion of the edge of the pixel. [Chemical 4]

In the formula (5), a plurality of R3's are each independently, and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent. m is an average value representing a number from 0 to 10, preferably less than one. [Epoxy compound having an anthracene skeleton] The epoxy compound having an anthracene skeleton is a compound having two epoxy groups in the anthracene skeleton, and specifically, it is preferably the following chemical formula (3) 11 200902579 Expressed as a compound.

[化5]

(3) The epoxy compound having a spider raft skeleton represented by the formula (3) has high heat resistance and chemical resistance due to the ruthenium structure. Therefore, by blending an epoxy compound having an anthracene skeleton, the heat sensitivity and chemical properties of the coloring photosensitive composition can be improved. [The carboxylic acid compound (a - 2 ) containing an ethylenically unsaturated group] The carboxylic acid compound (a - 2 ) containing an ethylenically unsaturated group preferably contains a propylene group or a mercapto propylene group in the molecule. A mono-vinyl carboxylic acid compound. Examples of such an ethylenically unsaturated group-containing carboxylate (a - 2 ) include acrylic acid, mercaptoacrylic acid, /3-styryl acid, /3-mercaptoacrylic acid, and α-cyanocinnamic acid. , cinnamic acid, etc. The ethylenically unsaturated group carboxylic acid compound (a-2) may be used singly or in combination of two or more kinds. As a method of reacting the above epoxy compound (a-1) with the ethylenically unsaturated carboxylic acid compound (a-2), a conventionally known method can be used. For example, the following methods may be mentioned: triethylamine, benzylethylamine tertiary amine, dodecyltrimethylammonium chloride, tetradecyl ammonium sulfate, tetraethylammonium chloride, benzyltriethyl a quaternary ammonium salt such as a vaporized ammonium, a pyridine, a triphenyl group or the like as a catalyst, and the epoxy compound (a-1) and the ethylenically unsaturated group are bonded to each other. 12

200902579 The carboxylic acid compound (a - 2 ) is reacted in an organic solvent at a temperature of from 50 to 150 ° C for several hours to several tens of hours. The ratio of the amount of the epoxy compound (a-1) to the reaction of the acid-containing (a - 2 ) containing ethylenically unsaturated groups, in the case of an epoxy compound (a - 1 epoxy equivalent and ethylidene-containing unsaturated) The ratio of the equivalent of the acid-lowering compound (a - 2 ) is usually 1:0 · 5 to 1: 2, preferably 1: 1 : 1. 2 5 , more preferably 1:1. When the ratio of the equivalent of the epoxy compound (a -1 epoxy equivalent to the ethylenically unsaturated group-containing tarenic acid compound (a - 2 )) is within the above range, the crosslinking efficiency tends to be improved. [Polyhydric anhydride (a-3)] As the polybasic acid anhydride (a-3), a compound containing at least two benzene rings as an acid anhydride of a carboxylic acid having two carboxyl groups can be used as such a polybasic acid anhydride ( Examples of a - 3 ) include an acid anhydride having a biphenyl skeleton represented by the following formula, and an acid anhydride having an organic group bonded to each of the benzene rings represented by the following formula (7). ) carboxylic acid, so the above. (6) of 2

〇 〇 II 4 II C—ΟΟ—R4—Ο—C

Ο (7) 13 200902579 [In the formula (7), R4 represents an exudation group which may have a substituent having 1 to 10 carbon atoms. At least two benzene rings can be introduced into the photopolymerizable compound (A) by using an acid anhydride of a carboxylic acid having two or more carboxyl groups.

Further, the polybasic acid anhydride (a-3) may contain other polybasic acid anhydrides in addition to the above-mentioned acid anhydride having at least two benzene rings. Examples of the other polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and mercaptohexahydroorthophenylene. Diphthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyrogallic anhydride, benzophenone tetradecanoic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methyl Hexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-mercaptotetrahydrobutanyl Anthracene anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride. These polybasic acid anhydrides may be used singly or in combination of two or more. As a method of reacting the epoxy compound (a-1) with the ethylenically unsaturated group-containing carboxylic acid compound (a-2) and further reacting with the polybasic acid anhydride (a-3), a previously known method can be used. . Further, the molar number of the OH group in the reaction of the epoxy compound (a-fluorene) with the carboxylic acid compound (a-2) containing the ethylenically unsaturated group, and the anhydride of the polybasic acid anhydride (a-3) The ratio of the equivalent ratio of the base is usually 1: 1 to 1: 0. 1, preferably 1: 0.8 to 1: 0.2. The molar number of the OH group in the reaction of the epoxy compound (a-fluorene) with the ethylenic unsaturated group-containing slow acid compound (a-2) and the acid anhydride group of the polybasic acid anhydride (a-3) The equivalent ratio is set within the above range, and the solubility of 14 200902579 in the developer tends to be moderate, which is preferable.

a resin (A1) obtained by reacting an epoxy compound (a-1) with a carboxylic acid compound (a-2) containing an ethylenically unsaturated group, and further reacting with a polybasic acid anhydride (a-3) The acid value is preferably from 10 to 150 mgKOH/g, more preferably from 70 to 110 mgKOH/g, based on the resin solid content. By setting the acid value of the resin (A1) to 10 mgKOH/g or more, sufficient solubility in the developer can be obtained. Further, by setting the acid value of the resin (A 1 ) to 150 mgKOH/g or less, sufficient curability can be obtained, and surface properties can be improved. Further, the weight average molecular weight of the resin (A 1 ) is preferably 1,0 0 0 to 1 5 , 0 0 0, more preferably 2,0 0 0 to 1 3 , 0 0 0. By setting the weight average molecular weight of the resin (A1) to 1,0 0 or more, heat resistance and film strength can be improved. Further, by setting the weight average molecular weight of the resin (A1) to 15 or less, sufficient solubility in the developer can be obtained. [The monomer containing an ethylenically unsaturated group] The photopolymerizable compound (A) used in the present invention preferably contains a monomer having an ethylidene group and a group. The monomer having an ethylenically unsaturated group may be a monofunctional monomer or a polyfunctional monomer. Examples of the monofunctional monomer include (mercapto) acrylamide, hydroxymethyl (meth) acrylamide, hydrazine. Oxymethyl (mercapto) acrylamide, ethoxylated (meth) acrylamide, propoxy fluorenyl (methyl) acrylamide, butoxy methoxy fluorenyl (fluorenyl) Acrylamide, N-hydroxydecyl (meth) acrylamide, N-hydroxyindenyl (decyl) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, cis-butane Alkylene dianhydride, itaconic acid, itaconic anhydride, thiconic acid, citraconic anhydride, crotonic acid, 2-propenylamine-2 - 15 200902579

Mercaptopropanesulfonic acid, tert-butyl propylene sulfanilide, methyl methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl methacrylate Ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (mercapto)acrylic acid 2 -Phenoxy-2-hydroxypropyl ester, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth) acrylate , (di) dimethyl (meth) acrylate, glycidyl (meth) acrylate, 2, 2, 2 - trifluoroethyl (meth) acrylate, 2, 2, 3, 3 (meth) acrylate - tetrafluoropropyl ester, (mercapto) acrylate half ester of phthalic acid derivative, and the like. These monofunctional monomers may be used singly or in combination of two or more. On the other hand, examples of the polyfunctional monomer include ethylene glycol di(decyl)acrylate, diethylene glycol di(decyl)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (fluorenyl) acrylate, polypropylene glycol bis(indenyl) acrylate, butanediol di(meth) acrylate, neopentyl glycol bis(indenyl) acrylate, 1,6-hexanediol di(a) Acrylate, trihydroxymercaptopropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2, 2- Bis(4-(indenyl)propenyldiethoxyphenyl)propane, 2,2-bis(4-(indenyl)propenyloxypolyethoxyphenyl)propane, (fluorenyl) 2-hydroxy-3-(2-methyl) acrylate Bing Xixi group, propyl glycol diglycidyl 16200902579

Glycerol ether di(meth)acrylate, diethylene glycol diglycidyl ether di(indenyl) acrylate, phthalic acid diglycidyl di(meth)acrylate, glycerin triacrylate, glycerol Glycidyl ether poly(indenyl) acrylate, amino decyl acrylate (ie, toluene diisocyanate), trimethyl hexamethylene diisocyanate, hexamethylene diisocyanate, etc. a reaction of 2-hydroxyethyl acrylate, anthracenyl bis(indenyl) acrylamide, (mercapto) acrylamide decyl ether, polyol and N-hydroxydecyl (decyl) acrylamide A polyfunctional monomer such as a condensate or triacryl forma 1 or the like. These polyfunctional monomers may be used singly or in combination of two or more. The amount of the monomer containing the ethylenically unsaturated group is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, based on the solid content of the coloring photosensitive composition. When the amount of the monomer containing the ethylenically unsaturated group is within the above range with respect to the solid content of the colored photosensitive composition, the balance of sensitivity, developability, and resolution tends to be easily obtained, which is preferable. The content of the photopolymerizable compound (A) is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, based on the solid content of the coloring photosensitive composition. When the content of the photopolymerizable compound (A) is within the above range with respect to the solid content of the coloring photosensitive composition, it is preferable to obtain a balance between sensitivity, developability, and analytical property. <Photopolymerization initiator (B) > As the photopolymerization initiator (B), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-mercapto-p-phenylpropane- ketone , 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-mercapto-1-propane-butanone, 1-(4-isopropylbenzene 17 200902579 base)-2 - Benzyl-methylpropan-I-oxime, 1-(4-h-dioxophenyl)-2-yl-2-ylidenepropan-I-one, 2,2-dimethoxy- 1,2-diphenylethen-1-one, bis(4-dimethylaminophenyl)one, 2-indenyl-:l-[4-(methylthio)phenyl]-2 - 2-methyib-1-(morphoinopropane-1-one), 2-benzyl-2-dimethylamino-1-() 4-Phenylphenyl)butane-butanone, ethyl ketone-bu [9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]-1- (0-acetamidine), 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylamine Benzophthalic acid, decyl 4-didecylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamine benzoate Base-2 -ethylhexyl ester, 4-didecylamino-2-isopentylbenzoic acid, benzyl-yS-decyloxyethyl acetal, benzyldimethylketal, 1-phenyl-1 ,2-propylenedione-2-(0-ethoxycarbonyl)anthracene, methyl 0-phenylmercaptobenzoate, 2,4-diethylthioxanthone, 2-air thioxanthone, 2 , 4 - Dimercaptothioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-air thioxanthene, 2,4-diethyl thioxanthene, 2-methylthioxanthene, 2 -isopropyl thioxanthene, 2-ethyl hydrazine, octamethyl hydrazine, 1, 2 - alum, 2,3 - diphenyl fluorene, azobisisobutyronitrile, peroxide醯, isopropyl peroxide, 2-mercaptobenzimidazole, 2-mercapto benzoxazole, 2-mercaptobenzoquinone. Sodium, 2-(0-phenylphenyl)-4,5-bis(metamethoxyphenyl)imidazolyl dimer, dibenzophenone, 2-benzophenone, p,p'-double (didecylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl- 4-methoxybenzophenone, benzoquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 18 200902579 benzoin butyl ether, acetophenone, 2, 2-diethoxyacetophenone, p-dimercaptoacetophenone, p-didecylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-pair Methylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-diox-4-phenyloxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diphenylguanidinone, amyl 4-didecylaminobenzoate, 9-phenyl acridine, 1,7-double- (9-Acridine)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-fluorenyl)propane, p-methoxy-3° well P-methoxy Triazine), 2, 4, 6-tris(trichloromethyl)-all three = well, 2-methyl-4,6-bis(trichloromethyl) all three _, 2-[2-(5-曱Furfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three-flavor, 2-[2-(furan-2-yl)vinyl]-4,6-bis (trioxane) The base is tris-, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-,4,6-bis(tris). And 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trimethylmethyl)-all-*, 2-(4-decyloxyphenyl)- 4,6-bis(trichloromethyl) is three. Well, 2-(4-ethoxystyryl)-4,6-bis(triseodecyl)-tetra-, 2-(4-n-butoxyphenyl)-4,6-bis (three Chloroguanidine) is three. Well, 2,4-bis-trichloroindolyl-6-(3-bromo-4-indolyloxy)phenyl, tris, 2,4-di-tris-methyl- 6-(2-bromo-4 -decyloxy)phenyl benzene, 2,4-bis-trichloroindolyl-6-(3-oxa-4-methoxy)phenylethylphenyl ternary, _, 4-bis- Tris-methyl-6-(2-bromo-4-indolyloxy)styrylphenyl is tris-fluorene or the like. These photopolymerization initiators may be used singly or in combination of two or more. Among them, in terms of sensitivity, it is particularly preferable to use a lanthanide initiator. The content of the photopolymerization initiator (B) is relative to the coloring photosensitive composition.

200902579 The solid fraction is preferably from 0.5 to 30% by mass, more preferably from 1 to 20 I. By setting the content within the above range, sufficient properties and chemical properties can be obtained, and the coating film forming ability can be improved to suppress the deterioration. <Colorant (C) > Examples of the colorant (C) include a light-shielding agent such as carbon black or titanium black, and may also be used: Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se. , various metal oxides such as Ca ' Sr ' Ba ' Pd ' Ag ' Cd ' In' Sn, Sb, Hg' Pb' Bi, and A1; composite oxide; metal sulfide sulphate; or metal carbonate Inorganic pigments. Among these colorants (C), it is preferred to use a black pigment. Black pigments include carbon black. As the carbon black, well-known carbon black such as channel black, furnace black carbon black, or lamp black can be used, and in particular, the groove black is excellent in hiding, so that it can be suitably used. Alternatively, a resin black carbon black can be used. Specifically, a carbon black and a resin reactive with a carboxyl group, a hydroxyl group, or a carbonyl group on the surface of carbon black are mixed, and the resin-coated carbon black obtained by heating at 380 degrees is used; or The monomer is dispersed in a water-organic solvent mixture or a water-surfactant mixture, and is subjected to radical polymerization or base copolymerization to obtain a resin-coated carbon black or the like in the presence of a polymerization initiator. Since the conductivity of the tree-coated carbon black is lower than that of the carbon black not coated with the resin, in the case of a color filter such as a liquid crystal display, it is possible to manufacture a low-power-consumption display with less leakage and high reliability. . As the coloring agent, it is also possible to add an organic pigment amount to heat-resistant light hardness to the above inorganic pigment. In addition, Mg, Si, and gold are used as black and optical coatings. 50~ Ethylene free grease is used as the auxiliary pigment. By appropriately selecting and adding an organic pigment which exhibits a complementary color of an inorganic pigment, the following effects can be obtained. For example, carbon black exhibits a reddish black color. Therefore, since the carbon black is added as an auxiliary pigment which exhibits a red complementary color, that is, a blue color, the red color of the carbon black disappears, and the whole body exhibits a better black color. The organic pigment is preferably used in an amount of from 10 to 80% by mass, more preferably from 20 to 60% by mass, even more preferably from 20 to 40% by mass, based on the total of the inorganic pigment and the organic pigment.

As the inorganic pigment and the organic pigment, a solution obtained by dispersing a pigment at an appropriate concentration using a dispersing agent can be used. For example, as the inorganic pigment, CF B 1 ack (carbon concentration: 20%), a carbon dispersion made of Royal Chinese pigment, CF Black (containing 24% of high-resistance carbon), Titanium black dispersion CF Black (containing 20% titanium black pigment) manufactured by National Pigment. In addition, examples of the organic pigment include a blue pigment dispersion liquid CFBlue (containing 20% blue pigment) manufactured by Yuki Co., Ltd., and a purple pigment dispersion liquid (containing 10% purple pigment) produced by Yuki Co., Ltd., and the like. . Further, as the dispersing agent, a polyethylene dispersant, a urethane resin or an acrylic resin dispersant is preferably used. The content of the colorant (C) is preferably from 10 to 70% by mass based on the solid content of the coloring photosensitive composition. By setting the content to 70% by mass or less, the photocuring failure can be suppressed, and by setting the content to 10% by mass or more, sufficient light blocking property can be obtained. Further, when the colored photosensitive composition of the present invention is used as a black matrix as described below, the concentration of the colorant (C) is preferably an OD per film thickness (Optical Density, 21).

The 200902579 optical density) value is adjusted by 1.5 or more. If the value of 0 D per 1 // thickness is 1.5 or more, a sufficient contrast can be obtained when it is used for the black color of the liquid crystal display. <Solvent> The colored photosensitive composition of the present invention preferably contains a solvent. Examples of the solvent include ethylene glycol monomethyl ether, alcohol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethyl ether monoether, diethylene glycol monoethyl ether, and diethyl ether. Glycol mono-n-propyl ether, di-n-butyl-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dimethyl dimethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl dipropylene glycol Monoterpene ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propylene dipropylene glycol mono-n-butyl ether, tripropylene glycol monoterpene ether, tripropylene glycol mono-(poly)alkylene glycol monoalkyl ether; ethylene glycol monomethyl ether Alkanediol monoalkane such as acid ester, ethylene diethyl ether acetate, diethylene glycol monoterpene ether acetate, diethylene glycol monoacetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate Ether ether acetate; diethylene glycol dioxime ether, diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; mercapto ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Ketones; alkyl lactate such as 2-hydroxypropionic acid ethyl 2-hydroxypropionate; 2-hydroxy-2-mercaptopropyl ester, 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxyethoxy acid methyl ester, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyethyl ester '2-hydroxy-3-mercaptobutyric acid Methyl ester, 3-mercapto-3-oxoxybutyl 3-acetoxybutyrate, ethyl 3-methyl-3-methoxybutyrate propionate, n-propyl acetate, isopropyl acetate Ester, n-butyl acetate, ethylene matrix, diluted ethylene glycol monool, single bond, ether, ether, etc., alcohol monoether B (poly) alcohol oxime ethyl ester, acid ethyl propionic acid, B, acetic acid 22 200902579 Butyl ester, n-amyl phthalate, isodecyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, decyl pyruvate, Other esters such as ethyl pyruvate, n-propyl pyruvate, decyl acetate, ethyl acetate, 2-ethyloxybutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; N-曱A guanamine such as a pyrrolidone, N,N-dimethylformamide or N,N-dimercaptoacetamide. These solvents may be used singly or in combination of two or more.

The content of the solvent is preferably from 50 to 500 parts by mass based on 100 parts by mass of the solid content of the coloring photosensitive composition. <Other components> The colored photosensitive composition of the present invention may contain an additive as needed. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a surfactant, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing agent, a dispersing aid, a filler, and a adhesion promoter. , antioxidants, UV absorbers, anticoagulants, etc. <Preparation method of coloring photosensitive composition> The colored photosensitive composition of the present invention can be obtained by mixing all of the above components with a stirrer. Further, it is also possible to filter using a filter to make the obtained mixture uniform. <Manufacturing Method of Color Filter> Hereinafter, a method of forming a color filter using the colored photosensitive composition of the present invention will be described. [Formation of black matrix] First, use a roll coater, a reverse coater, a bar coater, etc., contact 23 200902579 transfer type coating device, or spin coater (rotary coating device), shower curtain type A non-contact type coating device such as a coater applies the colored photosensitive composition of the present invention to a substrate. As the substrate, a substrate having light transmissivity is used.

Then, the applied colored photosensitive composition is dried to form a coating film. The drying method is not particularly limited. For example, any of the following methods may be used: (1) drying at a temperature of 80 to 1 20 ° C, preferably 90 to 100 ° C, using a hot plate. Method of 0 to 1 20 seconds; (2) Method of leaving at room temperature for several hours to several days; (3) Method of removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours. Then, the coating film is irradiated with an active energy ray such as ultraviolet rays or excimer laser light through a negative mask to perform partial exposure. The amount of the energy ray to be irradiated varies depending on the composition of the coloring photosensitive composition, and is preferably, for example, about 30 to 2,000 mJ/cm2. Then, the exposed film is developed with a developing solution, thereby forming a pattern of a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developer include an organic developer such as monoethanolamine, diethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt. Then, the developed pattern is post-baked at a temperature of about 200 °C. At this time, it is preferred to perform a full exposure of the formed pattern. By the above processing, a black matrix having a predetermined pattern shape can be formed. [Forming a color filter by lithography] Using a color-sensitive photosensitive composition containing a coloring agent of three primary colors of R, G, and B, for each color, the same method as the formation of the black matrix described above is used. A color filter can be formed by sequentially forming a color on the substrate on which the black matrix is formed. [Formation of Color Filter by Inkjet Method] From the inkjet head, inks of respective colors of R, G, and B are ejected to respective regions divided by the black matrix formed as described above, and ink accumulated by heating or light is used. hardening. Thereby, a color filter can be formed. [Examples] Hereinafter, examples of the invention will be described, but the invention is also set forth in the examples. <Synthesis of photopolymerizable compound> (Synthesis Example 1)

In a 500 ml four-necked flask, the bisphenolphthalein type epoxy resin represented by the following formula (8 is shown as 2 3 5 g (epoxy equivalent of 2 3 5 ) and ammonium tetrachloride 110 mg, 2, 6- Di-tert-butyl-4-mercaptophenol 100 mg dilute acid 72. 0g, one side is blown into the air at a rate of 25 ml / min, and is heated and dissolved at 90 ° to 0 0 ° C. Then, in solution It is slowly heated in a white turbid state, heated to 120 ° C, and completely dissolved. Here, the liquid gradually becomes transparent and viscous, and stirring is continued in this state. The acid value is measured, and heating and stirring are continued until the acid value It is less than mgKOH/g. It takes 12 hours for the acid value to reach the target value. Then, to room temperature, a colorless transparent and solid bisphenol oxime type epoxy propylene I is obtained.

[Chem. 7] Layer. The method is not limited to) 曱 及 and C, 溶, 1. 0 冷却 t酉. 25 200902579

Then, in the above-mentioned bisphenol borne epoxy propylene 307.0 g, 600 g of 3-methoxybutyl acetate was added, and the solution was mixed into benzophenone tetradecanoic dianhydride 80. 5 g and tetraethylammonium bromide were slowly warmed up and reacted at 110 ° 1 1 5 °C. Thereafter, the mixture was reacted with 1,2, tetrahydrophthalic anhydride (38. Og) and allowed to react at 90 ° C to obtain an A-1. The disappearance of the acid anhydride group was confirmed by infrared spectroscopy. The weight average molecular weight of the substance A-1 as measured by GPC was 5,000. (Synthesis Example 2) As an epoxy compound having a biphenyl skeleton, Epikote YX4000H (manufactured by Japan Epoxy Resins, epoxy equivalent: 192) represented by the following (9), 400 g, and trisylphosphine 4 g, 153 g of propylene and 600 g of 3-methoxybutyl vinegar acetate were mixed and reacted at 90 ° C. Thereafter, 40 g of tetrahydrophthalic anhydride and 360 g of tetrahydrophthalic acid dianhydride were added as a polybasic acid anhydride, and further reacted to obtain a compound A-2 having a biphenyl skeleton. The disappearance of the acid anhydride group was confirmed by an external spectrum. The compound A-2 had a weight average molecular weight of 700% as determined by GPC. [8] After acid ester L, 1 g, 3, 6-chemical compound formula company olefinic acid ^ 100 phenyl this obtained by red amount flat 26 200902579

(Synthesis Example 3)

Except that NC-3000 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 188) represented by the following chemical formula (10) was used as an epoxy compound having a biphenyl skeleton, and 650 g of acetic acid 3-oxime was used. Compound A-3 was synthesized in the same manner as in Synthesis Example 2 except for the butyl butyl ester. The weight average molecular weight of the compound A-3 as determined by GPC was 6,000. [Chemistry 9]

(Synthesis Example 4)

Compound A-4 was synthesized in the same manner as in Synthesis Example 2 except that epochene 82-type epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent: 190) 390 g was used as the epoxide. The weight average molecular weight of this compound A-4 as measured by GPC was 4,000. <Examples and Comparative Examples> With respect to the colored photosensitive compositions of the examples and the comparative examples, 150 g of the compounds A-1 to A-4 were used in the mass ratio shown in Table 1, and further, the mixer was used. It is combined with dipentaerythritol hexaacrylate 30g, ethyl ketone, 1-[9-ethyl-6-(2-mercaptophenyl)-9H-indazol-3-yl]-l-(0-acetamidine)肟) (trade name: IRGACURE 0XE 02 , Ciba Specialty Chemicals 27

200902579 Manufactured by the company) 1 2 g, mercaptobenzimidazole 6 g, 2,4-bis(yl)-6-(3-xi-4-decyloxy)phenyl tetra-spray 4 g, pigment liquid name: CF Black, containing 24% of carbon, manufactured by Royal National Colors Co., Ltd.) 3-methoxybutyl acetate 500 g was mixed for 2 hours, and then filtered with a 5 #m apparatus to prepare a colored photosensitive composition. [Table 1] Photopolymerizable compound (mass ratio) Example 1 Al/A-3 = 15/85 Example 2 Al/A-3 = 40/60 Example 3 Al/A-2-15/85 Example 4 Al/A-2 = 50/50 Example 5 A-2/A-3=85/15 Comparative Example 1 A-3 = 100 Comparative Example 2 Al = 100 Comparative Example 3 A-2=100 Comparative Example 4 A -4 = 100 Comparative Example 5 A - l/A-4 = 50/50 Comparative Example 6 A-2/A-4 = 50/50 Comparative Example 7 A-3/A-4 = 50/50 <pattern formation Method> Using a spin coater (TR2500: Tokyo Tokako Co., Ltd.), the examples and the comparative color photosensitive compositions were applied to a thickness of 1. 2 gm. On a clean surface substrate of 1 mm, it was dried at 90 ° C for 2 minutes to obtain a film (photosensitive layer) of coloring sensitivity. Then, the film was selectively irradiated with ultraviolet rays via a negative mask. Thereafter, 0. 5 mass% aqueous sodium carbonate solution, spray development for 60 seconds, thereby forming a black matrix B containing a line, and then baking in a circulating oven at 2 2 (TC for 30 minutes: i. The film thickness of each black matrix produced is 1. 0 # m. Exposure to trichloropyrene (commodity 700 g, Filtration [made], the glass composition of the material is taken at 2 5 ° C. The treatment is carried out. Light quantity system 28 200902579 Increased from 10 mJ/cm2 to 180 mJ/cm in units of 5 mJ: Development <Evaluation> [CD Sensitivity] In the pattern forming method described above, when the line width of the black mask pattern (line) formed by the Bias+1.0 pair of 20/zm mask is 20 // m+1, The exposure amount at this time is evaluated as the CD sensitivity and r. Since the coloring photosensitive composition in the present invention is a negative photoresist, the larger the exposure amount, the larger the CD (Critical Dimension). Generally, The target line width for mass production is the mask line width + 1 to m. If the pattern can be formed with a lower exposure amount, the exposure can be shortened to increase the production line. [Thin line adhesion] When the width is 8 / ZD1, the pattern is formed, and the adhesion of the pattern is evaluated by d observation. The pattern-free flaking is recorded as a Q with a small amount of pattern peeling off, but no problem in practical application. Sexuality] By SEM observation, the exposure is set to 6 The linearity of the line pattern of 5 mJ/cm 2 and the line width of 2 0 /z m was evaluated. The line pattern edge was marked as "good", and the unevenness was marked as "bad". [Contour after development] The outline shape of the pattern having an exposure amount of 65 mJ/cm 2 and a line width of 20 # m was evaluated by SEM observation. This pattern is the pattern before and after the baking treatment. The person who is roughly rectangular is said to be "good, but it is changed, so it is changed to 2 β, j SEM i; ◎, 〇. The development of the edge is good", 29 200902579 will produce undercuts etc. Those who form a rectangle are marked as "bad". [Pattern defect after development] A pattern defect having a line width of 20 μm formed by setting the exposure amount to 65 mJ/cm 2 was evaluated by SEM observation. This pattern is the pattern before development and after the post-baking treatment. [to the time until the undercut is generated]

The evaluation was performed for the time (seconds) from the appearance of the pattern to the generation of the undercut at the time of development. Specifically, the development was carried out every 5 seconds using the time at which the pattern was developed during the development, and the evaluation was performed by SEM observation. The evaluation results of the black matrix patterns of the above respective examples and comparative examples obtained in the above manner are shown in Table 2. [Table 2] CD sensitivity (mJ/cm2) Thin line adhesion pattern Linear development time After pattern development after pattern development until the undercut occurs (seconds) Example 1 65 〇Good good No 25 Example 2 60 〇 Good and good None 25 Example 3 65 〇 Very good and good No 30 Example 4 60 ◎ Very good and good No 30 Example 5 70 〇 Good and good There are some 25 Comparative Example 1 70 〇 Some bad defects No 20 Comparative Example 2 60 〇 Good bad 15 Comparative Example 3 70 〇 Some bad good No 20 Comparative Example 4 100 X Bad defect 10 Comparative Example 5 90 Δ Bad defect 10 Comparative Example 6 95 Δ Bad defect 15 Comparative Example 7 95 Δ Bad defect 15 Table 2 It is understood that this embodiment using an epoxy compound (a-1) containing a unit derived from an epoxy compound having a biphenyl skeleton and a unit derived from an epoxy compound having an anthracene skeleton, and a comparative example In contrast, CD sensitivity, fine line adhesion, pattern linearity, post-development contour, development pattern after 30200902579, and when the undercut is generated Aspects, the results are good. [Simple diagram description] None [Main component symbol description] None

Claims (1)

200902579 X. Patent application scope: 1. A color-sensitive photosensitive composition containing a photopolymerizable compound (photopolymerization initiator (B), and a color former (C), characterized in that an upper polymerizable compound (A) a resin (A1) obtained by reacting an epoxy compound (a-1) with an ethylenically unsaturated group of a slow acid compound (a-2) and further reacting with an acid anhydride (a-3); The epoxy (a-oxime) contains an epoxy compound having a biphenyl skeleton and an epoxy compound having a Cardo skeleton. 2. The coloring photosensitive composition as described in claim 1 The resin (A1) contains a reaction between the epoxy compound which has a biphenyl skeleton as the (a-Ι) component and the component (a-2), and further reacts with the component (a-3). And the obtained resin (A1) and a reaction product of the above-mentioned (a-2) component by the above-mentioned (a-Ι) component, and the above-mentioned (a-2) component, and the above (a-3 The resin (A 1 - 2 ) obtained by the reaction. 3. The coloring as described in claim 1 In the optical composition, the resin (A 1 ) contains an epoxy compound having a biphenyl skeleton as the component (a -1 ) and an epoxidation having an anthracene skeleton and the above component (a-2). a reactant (A 1 - 3 ) obtained by reacting the reaction with the above (a-3). A), the light containing B is a mixture of ruthenium, and its constituents, 1); oxidized), The coloring photosensitive composition as described in claim 1, wherein the epoxy compound having a biphenyl skeleton is a compound represented by the following chemical formula (1). ] [In the formula (1), a plurality of R1 are each independently, and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and m is an average value, and represents a number of 0 to 10, η represents an integer of 1 to 4]. 5. The colored photosensitive composition according to claim 1, wherein the epoxy compound having a biphenyl skeleton is a compound represented by the following chemical formula (2), [Chemical 2] [In the formula (2), m is an average value, which represents a number from 0 to 10]. 6. The colored photosensitive composition of claim 4, wherein the value of m is less than 1. The coloring photosensitive composition according to the first aspect of the invention, wherein the epoxy compound having an anthracene skeleton is a compound represented by the following chemical formula (3), 8. The colored photosensitive composition according to claim 1, wherein the acid value of the resin (A1) is converted into a solid content of 10 mgKOH/g to 150 mgKOH/g ° 9. The colored photosensitive composition according to Item 1, wherein the resin (A1) has a weight average molecular weight of 1,000 to 15,000. 10. The coloring photosensitive composition according to the first aspect of the invention, wherein the photopolymerizable compound (A) further contains a monomer containing an ethylenically unsaturated group. 1. The colored photosensitive composition according to claim 1, wherein the coloring agent (C) is a black pigment. 34 200902579 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: