TW200819912A - Colored photosensitive resin composition - Google Patents

Abstract

To provide a colored photosensitive resin composition capable of easily forming on a substrate a good black matrix pattern excellent in linearity, free of peeling and residues, and giving excellent display contrast. The colored photosensitive resin composition comprises a photopolymerizable compound (A), a photopolymerization initiator (B) and a colorant (C), wherein the photopolymerizable compound (A) comprises a resin obtained by reacting a reaction product of an epoxy compound (a-1) and an unsaturated group-containing carboxylic acid (a-2) with a polybasic acid anhydride (a-3), and the resin is a compound having a biphenyl skeleton.

Description

200819912 IX. Description of the Invention: [Technical Field] The present invention relates to a color-sensitive photosensitive wax composition, and more particularly to a colored photosensitive resin composition for forming black for use in a color filter A light-shielding film at a matrix or the like.

[Prior Art] In the case of a color method using a pigment, an electrodeposition method, or an inkjet method, a coloring composition (a coloring photosensitive resin to which a binder resin or a photopolymerization is added) is dried. Then, exposure and development are performed to form a film to form a pixel. For each color light sheet, the image composition forming such a color filter requires sufficient resolution, slag, etc. The dispersion shadow step is used. Therefore, it is often required to generate a residue or a stain, and the substrate for removing the sharpness of the edge of the pattern must be continuously enlarged, and gradually, for example, a black matrix-like light power is required. A method for producing an exposed partial color filter is known as a dye dispersion method, etc. The pigment dispersion method is obtained by dispersing a pigment with a dispersant or the like, and a photopolymerizable monomer or the like is coated on a glass substrate. , dry color pattern. Then, when heating is performed to repeat the steps to form the adhesion between the colored photosensitive resin used for the color factor and the substrate, and the low development residual method is formed, it is possible to supply the light to be removed in the developing step. It has sufficient solubility and formability. Moreover, in recent years, it has been required to have a large margin of development. It is found that the difference in the cross-linking density in the entire wavelength region of the light and the unexposed portion is very difficult; and even the exposed portion can be sufficiently hardened on the side of the light-irradiating surface, but there is a side on the substrate side. Unhardened problems, etc. Further, since a large amount of a black coloring agent which is insoluble in the developing liquid is blended in a large amount, there is a problem that the developing property is remarkably lowered. Therefore, in order to solve such a problem, a coloring photosensitive resin composition (see Patent Document 1) is disclosed, and a novolak epoxy acrylate having a carboxyl group is used as a binder resin.

Further, a coloring photosensitive resin composition (see Patent Document 2) is disclosed, and a reactant of a carboxyl group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound is used as the binder resin. Further, a colored photosensitive resin composition (see Patent Document 3) is disclosed, which comprises a polycarboxylic acid resin which is a reaction product of an epoxy compound having two epoxy groups and a monocarboxylic acid, and an acid anhydride. It is obtained by carrying out a reaction. [Patent Document 1] JP-A-2004-43573 (Patent Document 3) JP-A-2004-43573

[Problems to be Solved by the Invention] However, even in the resin compositions described in Patent Documents 1 to 3, the sensitivity is insufficient, the adhesion to the pixel is poor, and the resin is easily peeled off, and residue is likely to remain. Wait for the problem. Further, since the development margin is small, the problem that the exposure portion is peeled off and the edge of the pixel is shaken according to the development time has not been released. In view of the above, the present invention provides a colored photosensitive resin composition which can easily form a favorable black matrix pattern which is excellent in linearity, does not cause peeling or residue, and exhibits excellent contrast. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have found that the above-mentioned problems can be solved by applying a resin containing a functional group excellent in photoreceptivity to a photosensitive composition. The invention has been made. More specifically, the present invention provides the following.

The present invention provides a colored photosensitive resin composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a coloring photosensitive resin composition of a coloring agent (C), and the photopolymerizable compound ( A) is a resin obtained by reacting an epoxy compound (a-1) with a reaction product containing an unsaturated carboxylic acid (a-2) and further with a polybasic acid anhydride (a-3), and the resin has a biphenyl skeleton. Compound. [Efficacy] According to the colored photosensitive resin composition of the present invention, a compound having a biphenyl skeleton is used as a raw material of the resin contained in the photopolymerizable compound in the colored photosensitive resin composition. Therefore, since the coloring photosensitive resin composition has a biphenyl skeleton, it is possible to provide a colored photosensitive resin composition which is excellent in balance between sensitivity and solubility, sharpness of the edge of the pixel, and excellent adhesion to the substrate. Further, it is possible to easily provide a color filter for a liquid crystal display with a high contrast and a beautiful color of R, G, and B. [Embodiment] [Better Mode for Carrying Out the Invention] Embodiments of the invention. The colored photosensitive resin composition (hereinafter also referred to as "composition") of the present invention contains a photopolymerizable compound (A), a photopolymerization agent (B), and a color former (C). [Photopolymerizable Compound (A)]

The photopolymerizable compound (hereinafter also referred to as "(A) component" contains a reaction product of the epoxy compound (a-1) and the unsaturated group-containing carboxylic acid (a-2), and further with a polybasic acid anhydride (a-3). The resin obtained by the reaction, and the resin is a compound having a stupid skeleton. The respective components will be described below. <Epoxy compound (al)&gt; The epoxy compound used in the present invention (hereinafter also referred to as (a-) 1) Component) An epoxy compound having a biphenyl skeleton is preferred. The compound having a biphenyl skeleton has at least one or more biphenyl skeletons represented by the following formula (5) in the main chain, and has one or more Further, the (a-1) component is preferably one having two or more epoxy groups. By using an epoxy compound having a biphenyl skeleton, since it has a bond in the photopolymerizable compound after the reaction. The benzene skeleton is a color-sensitive photosensitive resin composition which is excellent in balance of sensitivity and solubility, and has excellent sharpness and adhesion at the edge of the pixel. 200819912 [Chemical Formula 1]

(5)

(wherein a plurality of R3 groups each independently 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 1 represents an integer of 1 to 4) The biphenyl type epoxy resin is not particularly limited, and examples thereof include an epoxy compound represented by the following formula (1). [Chemical Formula 2]

(wherein the plural R1 groups each independently 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 η represents an integer of 1 to 4) In the formula (1), an epoxy compound represented by the following formula (2) is preferably used. By using the compound of the formula (2), it is possible to provide a composition excellent in balance of sensitivity and solubility. [Chemical Formula 3] 9 200819912

Further, in the formulas (1) and (2), m is an average value and represents the number of 0 to 10. The m is preferably less than 1. &lt;Unsaturated decanoic acid (a_2)&gt;

The unsaturated carboxylic acid (hereinafter also referred to as "(a-2) component)" used in the present invention contains reactivity such as an acrylic group and a methacrylic group in the molecule. The monocarboxylic acid of the unsaturated double bond is preferred. Examples of such an unsaturated group-containing carboxylic acid include acrylic acid, methacrylic acid, anthracene styryl acrylic acid, mercaptoacrylic acid, cyano cinnamic acid, and cinnamic acid. Further, the component (a-2) may be used singly or in combination of two or more. The epoxy compound (a-1) and the unsaturated group-containing carboxylic acid (a-2) can be synthesized by a well-known method. For example, the epoxy compound (a-1) and the unsaturated group-containing carboxylic acid (a-2), a tertiary amine such as triethylamine or benzylethylamine, or dodecyltrimonium chloride may be mentioned. 4th ammonium salt such as tetraammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, acridine or triphenylphosphine as catalyst, in organic solvent at reaction temperature 5 0~1 5 0 The method of °C reaction number to tens of hours. The amount of the component (a-1) and the component (a-2) used in the reaction, the ratio of the epoxy equivalent of the component (a·1) to the carboxylic acid equivalent of the component (a-2) is usually 1:0.5 to 1 : 2, with 1: 0.8~1: 1.25 is better, and 1:1 is better. When the ratio of the (a-Ι) component to the component (a-2) is from 1:0.5 to 1:2, 10 200819912 has a tendency to improve the crosslinking efficiency, and is preferable to D. Anhydride (a-3)&gt;

The polybasic acid anhydride (hereinafter also referred to as "(a-3 component)") is a polybasic acid anhydride having two or more carboxyl groups. The polybasic acid anhydride is not particularly limited, and examples thereof include maleic anhydride, acacia acid, iconic anhydride, acetic anhydride, tetrahydrogenic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrogen. Anthraquinone anhydride, trimellitic anhydride, pyrogallanoic anhydride, diphenylketone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethylhydrohydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, lower The compounds represented by the formulas (3) and (4). Further, these (a-3) components may be used singly or in combination of two or more.

[Chemical Formula 4]

(3) 11 200819912

(wherein R2 represents an alkylene group which may have a substituent having 1 to 10 carbon atoms)

Further, the component (a-3) is preferably a compound having two or more benzene rings. Among the above compounds, a compound containing at least one of the compounds represented by the formulae (3) and (4) is preferred. By using a resin synthesized from a polybasic acid anhydride having two or more benzene rings, it is possible to provide a colored photosensitive resin composition having excellent balance of sensitivity and solubility. A method known as a method of reacting the (a-Ι) component with the component (a-2) and reacting with the component (a-3) can be carried out by a known method. Further, the ratio of use is such that the molar ratio of the OH group in the component after the reaction between the component (a-1) and the component (a-2) and the acid anhydride group of the component (a-3) is usually 1: 1~1: 0·1, preferably 1: 0.8~1: 0·2. By setting it in the above range, the solubility in the developing solution tends to be appropriate, which is preferable. In addition, the acid value of the resin obtained by reacting the photopolymerizable compound (a-1) component, the component (a-2), and the component (a-3) is 10 mg KOH/g in the case of the resin solid component. The above 150 g/g is preferred, and more preferably 70 mg KOH/g or more and 110 mg KOH/g or less. By making the acid value of the resin 10 mg KOH/g or more, sufficient solubility can be obtained in the developing solution; and by making the acid value 150 gram [01 / gram or less, 12 200819912 can be obtained. It has a hardenability and can make the surface properties good. Further, the weight average molecular weight of the resin is preferably 1,000 or more and 40,000 or less, and more preferably 2,000 or more and 30,000 or less. By setting the weight average molecular weight to 1,000 or more, heat resistance and film strength can be improved. Further, by 4000 or less, sufficient solubility can be obtained in the developing solution. &lt;Monomer having an ethylenically unsaturated group&gt;

The colored photosensitive resin composition of the present invention preferably contains a monomer having an ethylenically unsaturated group as a photopolymerizable compound. The above monomer having an ethylenically unsaturated group preferably has a plurality of polymerizable functional groups. By containing a monomer having an ethylenically unsaturated group, the film strength of the formed film or the adhesion to the substrate can be improved. The monomer having an ethylenically unsaturated group may, for example, be a monofunctional monomer or a polyfunctional monomer. Examples of the monofunctional monomer include (meth)acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (decyl) acrylamide, and ethoxylated fluorenyl (fluorenyl). Acrylamide, propoxymethyl (meth) acrylamide, butoxy methoxymethyl (meth) acrylamide, acrylic acid 'maleic acid, maleic anhydride, itaconic acid , itaconic anhydride, citraconic acid, citric anhydride, crotonic acid, 2 _ propylene phthalamide-2-mercaptopropane sulfonic acid, t-butyl acryl decyl sulfonic acid, methyl (meth) acrylate, (methyl Ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl) ) 2-hydroxybutyl acrylate, 2-phenoxy-2 hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy 2-hydroxy 13

200819912 Propyl ester, glycerol mono(meth)acrylate, dimethylamine (meth)acrylate, propyl methacrylate, (2,2,2·3 a fluoroethyl ester, a bis(indenyl) acrylate of a 2,2,3,3-tetrafluoropropyl (meth) acrylate derivative, N-hydroxymethyl (meth) propyl, etc. Further, these may be separately Two or more types may be used in combination, and the polyfunctional monomer may, for example, be ethylene glycol di(methacrylate), diethylene glycol di(meth)acrylate or tetraethylene glycol di(methyl). Ester, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)ester, butanediol di(meth)acrylate, neopentyl glycol di(meth)ester, 1,6-hexanediol II (meth) acrylate, trimethylolpropane triacrylate, glycerol di(meth) acrylate, neopentyl alcohol tripropylene roasted neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, two Alcohol hexaacrylate, dipentaerythritol bis(indenyl) acrylate, neotris(decyl) acrylate, pentaerythritol tetrakis(meth) acrylate, Alcohol penta(indenyl) acrylate, dipentaerythritol hexakis(propylene) propylene 2,2-bis(4-(indolyl)propenyloxydiethoxyphenyl)propane, (4-(A) Acryloxypolyethoxyphenyl)propane, 2-hydroxy-3 propyleneoxypropyl (meth) acrylate, ethylene glycol dimethacrylate (meth) acrylate, diethylene glycol Dicyclopropyl ether di(meth)acrylic acid diepoxypropyl ester di(meth)acrylate, glycerol tripropylene glycerol polyepoxypropyl ether poly(meth) acrylate, (meth) propylene a reaction product of a formate (i.e., toluene diisocyanate), trimethylhexamethylene acid ester, and hexamethylene diisocyanate with 2-hydroxyl (meth)acrylate, methylene bis (methyl) ) acrylamide, (meth) acrylate, (methacrylic acid, acrylamide oxime I), propyl acrylate, acrylic acid, acrylic acid (methyl), acid ester, neopentyl pentaerythritol dipivalic acid Cool, 2,2-bis-(methyl) ether diester, acid ester, acid amine diisocyanoethyl ester decylamine 14 200819912 methyl ether, polyol and N-hydroxyindole ( The polyfunctional monomer yl) acrylamide of condensate, or tri propylene methylal etc. Also, these may be used alone, but also be used in combination of two or more.

The content of the monomer having an ethylenically unsaturated group is preferably 5% by mass or more and 50% by mass or less based on the solid content of the coloring photosensitive resin composition, and is preferably 10% by mass or more and 40% by mass or less. Better. It is preferable to have a tendency to be easily obtained by the balance of sensitivity, development, and resolution in the above range. [Photopolymerization Initiator (B)] Further, a photopolymerization initiator (hereinafter also referred to as "(B) component") includes acetophenone, 2,2-diethoxyethyl benzene, and dimethylene. Ethyl benzene, p-dimethylamino propyl benzene, dichloro ethane benzene, trichloro ethane benzene, acetophenone such as t-butyl acetonitrile, or diphenyl ketone, 2 - Diphenyl ketones such as chlorodiphenyl ketone, p-p-didimethylaminodiphenyl ketone, or benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzene Benzoyl ethers such as isobutyl ether, or benzyldimethylketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2- a sulfur compound such as isopropyl thioxane or an anthracene such as 2-ethyl hydrazine, octadecyl hydrazine, 1,2-benzopyrene or 2,3-diphenyl hydrazine, or an azo Organic peroxygen such as diisobutyronitrile, benzoquinone peroxide or cumene peroxide, or 2-hydrothiobenzimidazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzothiazole, etc. a thiol compound, or an imidazolyl compound such as 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, or Oxy triple well ttriazine) and three other compounds, or 2,4,6-reference (trichloromethyl) -s- 15 200819912

Triterpenoid, dimethyl-4,6-bis(trichloromethyl)-5-trimethyl, 2-[2-(5-methylfuran-2-yl)vinyl]- 4,6-bis ( Trichloromethyl)-b-trimium, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tripper, 2-[2-(4 -diethylamino-2-mercaptophenyl)vinyl]-4,6-bis(trichloromethyl)-s-triterpene, 2-[2-(3,4-dimethoxyphenyl) )vinyl]-4,6-bis(trichloromethyl)-S-tripper, 2-(4-methoxyphenyl)-4,6-bis(trichloroindenyl)-5-triterpene , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-b-trimium, 2-(4-n-butoxyphenyl)-4,6-bis (three a trimethyl hydrazine compound having a halomethyl group such as chloromethyl)-s-three-spray, or 2-benzyl-2-dimethylamino-1 - (4-nolphqlino phenyl)-butane-1 An aminoketone compound such as hydrazine. These photopolymerization initiators may be used singly or in combination of two or more. The content of the photopolymerization initiator is preferably from 1 part by mass to 150 parts by mass, preferably from 5 parts by mass to 100 parts by mass, based on 100 parts by mass of the solid component other than the solvent, and is preferably 10 parts by mass. 50 parts by mass is more preferred. By setting the content to 150 parts by mass or less, sufficient heat resistance and chemical resistance can be obtained, and when the content is 1 part by mass or more, the coating film formation performance can be improved and the photocuring failure can be suppressed. [Colorant (C)] The coloring photosensitive resin composition of the present invention contains a coloring agent (hereinafter also referred to as "(C) component"). The coloring agent may, for example, be a compound classified as a pigment in a colorimetric index (CI; issued by The Society of Dyers and Colourists), specifically, using the colorimetric index (CI) described below. 16 200819912 The number is better. C · I · Pigment Yellow 1 (hereinafter, "C · I · Pigment Yellow" is the same, only the number is recorded), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24' 31, 53, 55 , 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117 , 119, 120' 125, 126, 127, 128, 129 &gt; 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155,

156, 166, 167, 168, 175, 180, 185; CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same, only the number is recorded), 5, 13, 14, 16, 17, 2 4, 3 4, 36 , 38, 40, 43, 46' 49, 5, 55, 59, 61, 63, 64, 71, 73; CI·Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, only the number is recorded), 19' 23 '29, 30, 32, 36, 37, 38, 39, 40, 50;

CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, only the number is recorded), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18 , 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 ··1,48 ·· 2,48 ·· 3,48 ·· 4,49 : 1,49 ·· 2, 50 : 1, 52 : Bu 53 : : Bu 5 7 , 57 : : 1~ 5 7:2 , 58 : 2 , 58 : 4 , 60:1 , 63 : 1, 63 : 2 , 64 · · 1 ' 81 · · 83 , 88 , 90 · · 1 '97 , 101 , 102 , 104 , 105 106 ' 108 , 112 , 113 &gt; 114 ' 122 , 123 , 144 , 146 , 149 X 150 , 151 ' 155 ' 166 , 16 8 , 170 , 171 , 172 , 174 , 175 176 ^ 177 , 178 &gt; 179 , 1 80 , 185 , 187 ' 188 &gt; 190 ' 192 ' 193 , 194 , 202 ' 206 ' 207 , 208 ' 209 ' 215 , 216 , 217 , 220 , 223 , 224 , 226 , 227 ' 228 , 240 , 17

200819912 242, 243, 245, 254, 255, 264, 265; CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, only code), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, CI Pigment Green-7, CI Pigment Green-36, CI Pigment Green-37; CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, Pigment Brown 2 8; C · I. Pigment Black 1, C. I. Pigment Black 7. Further, when a black matrix is formed, the component (C) is made of a black pigment, and the black pigment is preferably carbon black. Further, metal oxides, composites, metal sulfides, metal sulfates or metal carbonates such as titanium black, copper, manganese, cobalt, chromium, nickel, zinc, calcium, and silver may also be mentioned. Among these pigments, carbon black having a high light-shielding property is more preferable. By using the above-mentioned photopolymerizable compound, it is possible to obtain a color-sensitive photosensitive material having high adhesion and excellent image retention even when a black pigment having a high light-shielding property is used. For carbon black, carbon black such as channel black, furnace black, hot black, and lamp black can be used. Further, it is particularly preferable to use a grooved carbon black having excellent light shielding properties. The resin can also be coated with carbon black. When the resin-coated carbon black is compared with the carbon black which is not coated with the resin, the electrical properties are low. Therefore, when a black matrix of a liquid crystal display element such as a liquid crystal display is used, it is possible to manufacture a low power consumption with low leakage and high reliability. The above organic pigment may be appropriately added as an auxiliary pigment to adjust the color tone of the carbon black. No. 66; C.I. Good. Iron, oxidized black, also known as the group, the display of the guide, using 18 200819912, a dispersant for uniformly dispersing the colorant to use polyamidene, urethane A resin-based or acrylic resin-based polymer dispersant is preferred, and in particular, when carbon black is used as the colorant, the dispersant is preferably an acrylic resin.

Further, each of the inorganic pigment and the organic pigment may be used singly or in combination of two or more kinds thereof, and in combination with the total amount of the inorganic pigment and the organic pigment in an amount of 100 parts by mass, and the organic pigment is preferably used in an amount of from 10 parts by mass to 80 parts by mass. It is preferably in the range of 20 parts by mass to 40 parts by mass. The inorganic pigment and the organic pigment are preferably dispersed in a photosensitive resin composition after being dispersed in a solution having a suitable concentration using a dispersing agent. In addition, the amount of the coloring agent used in the coloring photosensitive resin composition of the present invention is preferably 5% by mass or more and 70% by mass or less, and preferably 25% by mass or more and 55% by mass based on the solid content of the coloring photosensitive resin composition. % or less is preferable, and more preferably 30% by mass or more and 50% by mass or less. It is preferable that the black matrix or the respective colorant layers can be formed in the target pattern by the above range. In particular, when a black matrix is formed, it is preferred to adjust the amount of the black pigment in the coloring photosensitive resin composition so that the OD value per film thickness of 1 μm is 4 or more. In the black matrix, if the value of 00 per film thickness of 1 μm is 4 or more, a sufficient display contrast can be obtained when a black matrix as a liquid crystal display is used. [Other Ingredients] The colored photosensitive resin composition of the present invention can be added as needed according to the preparation of the compound. Specifically, there are sensitizers, hardening accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like. Further, the photosensitive resin composition of the present invention may be added with a solvent for dilution, a thermal polymerization inhibitor, an antifoaming agent, a surfactant, or the like.

Here, examples of the solvent which can be added to the coloring photosensitive resin composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and B. Glycol-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl mystery, diethylene glycol mono-n-propyl bond, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl mystery, di- propylene glycol monomethyl ether, di-propanol (poly) of ethyl ether, dipropylene glycol mono-n-propyl ether, di-n-propylglycol-n-butyl ether, tri-n-propylglycol monomethyl ether, tri-n-propylglycol monoethyl ether Alkyl glycol monoalkyl ethers; ethylene glycol monodecyl ether acetate 'ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl (poly)alkylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol didecyl ether, digan Alcohol methyl ethyl ether, two Other ethers such as alcohol diethyl ether and tetrahydrofuran; ketones such as mercaptoethyl ketone, cyclohexane, 2-heptanone, 3-heptanone; 2-hydroxylpropionate, 2-hydroxypropionic acid Alkyl lactate such as ethyl ester; ethyl 2-hydroxy-2-mercaptopropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl ester, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, decyl 2-hydroxy-3-methylbutanoate, 3-mercapto-3-methoxy butyl Acetic acid 20

200819912 Ester, 3-methyl-3-methoxybutylpropionate, ethyl acetate, isopropyl n-propyl acetate, n-butyl acetate, isobutyl acetate, isoamyl decanoate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyrate, n-butyl butyrate, decyl pyruvate, ethyl pyruvate, acetone propyl ester, methyl acetate methyl acetate, ethyl hydrazine Other esters such as ethyl acetate and 2-oxobutyric acid; aromatic hydrocarbons such as toluene and xylene; N-methylrrolidone, N,N-dimethylformamide, and N,N An amine such as dimethylacetamide. These solvents may be used alone or in combination of two or more. Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monoacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate diethylene glycol dimethyl ether, diethylene glycol decyl ethyl ether Cyclohexanone and 3-butylbutyl acetate are excellent in solubility in photopolymerizable compounds and photopolymerization, and are excellent in insoluble components such as pigments. It is particularly preferable to use propylene glycol monomethyl ether acetate 3-methoxybutyl acetate. The total amount of the photopolymerizable compound polymerization initiator and the coloring agent is 10 parts by mass, and the solvent can be used in a range of from 500 parts by mass to 500 parts by mass. Further, as the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether or the like can be used. The antifoaming agent may be a stone-based or fluorine-based compound; and the surfactant may be formed by various known interface activities such as a cation, a cation, or a nonionic system, and when the colored photosensitive resin composition of the present invention is used. Hereinafter, the colored photosensitive dendrimer of the present invention is applied onto a substrate and dried to form a film. In order to improve the physical properties of the coating hardening at this time, in addition to the above components, a macromolecular ester, a mercaptoether ester of n-ethyl acetate isophthalate, a methoxy-dispersible ester, and an optical ^ may be further included. 50, ionic agent. Patterns of lipids, and adhesions 21 200819912 agents as binders. The binder can be appropriately selected for the purpose of improving compatibility such as compatibility, film formability, developability, and adhesion. The thickness of the black matrix formed on the substrate can be generally set in the range of 1 μm to 10 μm, preferably 1.5 μm to 8 μm, and more preferably 2 μm to 5 μm. When the thickness is 1.5 μm or more, not only a black matrix which is a usual color filter but also a black matrix which is an ink jet type color filter can be used.

The colored photosensitive resin composition of the present invention can be obtained by mixing the above components using a stirrer. Further, it is also possible to filter by using a filter to make the obtained mixture uniform. [Method of Forming Color Filter] Hereinafter, a method of forming a color filter using the colored photosensitive resin composition of the present invention will be described. &lt;Formation of Black Matrix (Black Colored Layer)&gt; First, the colored photosensitive resin composition of the present invention (black-containing coloring agent) is subjected to contact transfer using a roll coater, a reverse roll coater, and a bar coater. A non-contact type coating device such as a coating device or a rotator (rotary coating device) or a curtain coater is applied onto a substrate. A substrate having light transparency can be used as the substrate. In order to improve the adhesion of the glass substrate to the colored photosensitive resin composition, a decane coupling agent may be applied to the glass substrate in advance. Alternatively, a decane coupling agent may be added in the preparation of the colored photosensitive resin composition. After coating the colored photosensitive resin composition, it is dried to remove the solvent.

200819912 agent. The drying method is not particularly limited. For example, the following method can be used. (1) Drying at 60 ° C or more and 120 ° C or less on a hot plate, preferably at a temperature of 10 ° C or less, drying 60 seconds to 1 2 0 The method of placing the second at room temperature for several hours to several days, (3) placing the gas in the warm air heater for several ten minutes to several hours to remove the solvent, and then placing the negative mask in the middle, illuminating Partial exposure is performed by active energy lines such as ultraviolet light and light. The irradiation is different depending on the composition of the photosensitive resin composition, and is preferably, for example, about 2000 mJ/cm2. Next, the exposed film is developed by a developing liquid to form a desired shape. The development method is not particularly limited, and for example, a monthly spray method or the like can be employed. Examples of the developing solution include organic substances such as monoethanolamine, diethanolamine, and amine, or aqueous solutions of sodium hydroxide, potassium hydroxide, carbonic acid, and a 4-grade salt. Next, the developed pattern is formed at about 200t to form a black matrix. Further, the black matrix formed by uniformly exposing the formed pattern can be used as a spacer or an ink jet partition depending on the pattern shape and thickness. (1) Forming a color filter by a lithography method On the substrate on which the black matrix is formed, a coloring photosensitive resin composition containing a coloring agent of three primary colors of G and B is used, and the black matrix is similarly This is formed in sequence to form a color filter. (2) Forming a color filter by inkjet method Any one of the methods is 90 〇C by method, (2) or infrared method. The amount of excimer lightning energy line 3 0 m J / c m 2 is required to be I-impregnation method, sodium triethanolate, ammonia, baking, and preferably. The difference is usually R, , and the formation of the color layer. Borrow 23

200819912 In the case of forming a color filter by an inkjet method, an inkjet-type luxury gold or a partition wall (hereinafter referred to as a partition wall) formed by using a colored photosensitive resin composition. Because the partition wall is black more &amp; * ί〇] to achieve the task as a black matrix. Specifically, first, the inks of R, G, and Β are accumulated in the partition wall by the portion surrounded by the above-mentioned partition wall.鸯箸, or light hardens the accumulated ink. Thereby, it is possible to form a color/bar light [Examples] [Example 1] 400 g of EPICOAT ΥΧ 4000 混合 (as a bis-epoxy compound, JAPAN EPOXY RESIN company &gt; 192), 4 g 3 Phenylphosphine, 15 3 g of acrylic acid, and 6 〇()t butyl acetate, and at 90 to 10 〇. (: The reaction is carried out. With 40 g of tetrahydrophthalic anhydride and 3 60 g of biphenyl tetracarboxylic anhydride, the reaction is carried out to obtain a resin A having a biphenyl skeleton. The mass average molecular weight measured by GPC 70 〇〇, mg KOH/g. Mix 150 g of the above resin a, 30 g of dipentaerythritol vinegar, 12 g of 1-[9-ethyl-6-(2-methylbenzhydryl) _91!-咔 咔 乙 ketone small (0-acetamidine) (trade name: IRGACURE OXE 02 SPECIALTY CHEMICALS company), 6 grams of thiosulfonylbenzo 4 grams 2,4 bis (trichloromethyl)-6 -(3-Bromo-4-indolyl)phenyl-s-three-gram pigment liquid (trade name: CF black, carbon black 24%, and the film of the royal pigment can form a film. Gas equivalent•Field/ - -_ Anhydride, Intestinal A, F is 9 〇 〇 -3 -3 - 】], CIBA ϋ ϋ, and ' 7000 system, 24 200819912 5 0 0 3 · methoxybutyl Acetate to prepare a colored photosensitive resin composition 0 [Example 2]

Except for 520 g of 14 €:-3000 (as an epoxy compound having a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 188), and 650 g of 3-methoxybutyl acetate, and examples 1 was carried out in the same manner to synthesize resin hydrazine. The resin oxime has a molecular weight of 6000 and an acid value of 90 gram/g. This resin ruthenium was used to prepare a colored photosensitive resin composition. [Example 3] Resin C was synthesized in the same manner as in Example 1 except that only 420 g of biphenyltetracarboxylic dianhydride was used as the polybasic acid anhydride. The resin C had a molecular weight of 29,000 and an acid value of 100 g KOH/g. This resin C was used to prepare a colored photosensitive resin composition. [Comparative Example 1] Resin D was synthesized in the same manner as in Example 1 except that EPICOAT 828 (manufactured by JAPAN EPOXY RESIN Co., Ltd., epoxy equivalent 190) of 3 90 g of bisphenol A type epoxy resin was used as the epoxy compound. . The resin D had a molecular weight of 4,000. This resin 0 was used to prepare a colored photosensitive resin composition. [Comparative Example 2] The same procedure as in Example 1 was carried out except that 500 g of a dicyclopentadiene type epoxy resin 25 200819912 (epoxy equivalent 283) represented by the following formula (6) was used as the epoxy compound. Synthetic resin E. The molecular weight of the resin E was 4,500. This resin E was used to prepare a colored photosensitive resin composition. [Chemical Formula 5]

The formation of the black matrix is performed as follows.

The colored photosensitive resin compositions of the examples and the comparative examples were applied on a glass substrate, and baked at a thickness of 1.5 μm for 9 seconds at TC for 120 seconds. Subsequently, the formed film was exposed through a photomask (exposure) The amount is changed in the range of 50 to 120 mJ/cm 2 ), and an alkali developing solution (trade name: N-A3K, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used for image formation (change in the range of development time of 45 to 70 seconds) to form a pattern. Subsequently, the formed pattern was post-baked at 220 ° C for 30 minutes using a circulating oven to form a black matrix having a line width of 10 μm. Further, when the black matrix was formed, the exposure amount shown in Table 1 was used. (Evaluation) The colored photosensitive resin composition prepared in the above Examples and Comparative Examples and the black matrix formed were examined for pattern linear advancement and sensitivity, and 26 200819912 and the coated colored photosensitive resin composition. The results are shown in Table 1. The evaluation method is as follows: Pattern linear advancement (linear advancement): visually judge whether the edge of the formed 10 μm line is shaken, and when it is not shaken, it is shaken. When it is moving, it is X. Adhesiveness: It is 〇 when there is no peeling and defect in the exposed part, and X when there is peeling and defect.

Residue: 显 when there is no residue in the unexposed part after development, and foreign matter when X 〇 is applied when there is residue: Applying the colored photosensitive resin composition on a glass substrate (550 X X 650 亳 meters), calculate immediately The number of foreign matters on the formed film was determined by the average value after coating on 20 glass substrates. [Table 1] Development time (seconds) Exposure amount (mJ/cm2) Foreign matter (unit) 50 80 100 120 Linear advancement Adhesive residue Linear advancement Adhesive residue Linear advancement Adhesive residue Linear advancement Adhesive residue implementation Example 1 45 〇〇〇〇〇〇〇〇〇〇〇〇1.5 50 〇〇〇〇〇〇〇〇〇〇〇〇55 〇〇〇〇〇〇〇〇〇〇〇〇· 60 XX 〇〇〇〇〇 〇〇〇〇〇70 XX 〇〇〇〇〇〇〇〇〇〇Embodiment 2 45 〇〇〇〇〇〇〇〇〇〇〇〇1.4 50 〇〇〇〇〇〇〇〇〇〇〇〇55 XX 〇 〇〇〇〇〇〇〇〇〇60 XX 〇〇〇〇〇〇〇〇〇〇70 XX 〇〇〇〇〇〇〇〇〇〇Example 3 45 〇〇〇〇〇〇〇〇〇〇〇〇1.4 50 〇〇〇〇〇〇〇〇〇〇〇〇55 〇〇〇〇〇〇〇〇〇〇〇〇60 XX 〇〇〇〇〇〇〇〇〇〇70 XX 〇〇〇〇〇〇 〇〇〇〇Comparative example 1 45 XX 〇〇〇〇〇〇〇〇〇〇1.9 50 XX 〇XX 〇〇〇〇〇〇〇55 XX 〇XX 〇XX 〇〇〇〇60 XX 〇XX 〇XX 〇XX 〇 70 XX 〇XX 〇XX 〇XX 〇27 200819912 Comparative Example 2 45 XX 〇XX 〇XX 〇〇〇〇4.3 50 XX 〇XX 〇XX 〇XX 〇55 XX 〇XX 〇XX 〇XX 〇60 XX 〇XX 〇XX 〇 XX 〇70 XX 〇XX 〇XX 〇XX 〇 According to Table 1, a colored photosensitive resin composition using a photopolymerizable compound having a biphenyl skeleton can have (increased) development margin and can form sensitivity. A light-shielding film that is high and has a straight line pattern.

[Simple diagram description] None [Main component symbol description] None

28

Claims (1)

200819912 X. Patent application scope: 1. A colored photosensitive resin composition comprising a photopolymerizable compound (A), a photopolymerization initiator (B), and a coloring agent (C) colored photosensitive resin composition, The photopolymerizable compound (A) contains a resin obtained by reacting an epoxy compound (a-1) with a reaction product containing an unsaturated carboxylic acid (a-2) and a polybasic acid anhydride (a-3), and This resin is a compound having a biphenyl skeleton. 2. The colored photosensitive resin composition according to claim 1, wherein the epoxy compound (a-1) is a compound having a biphenyl skeleton. 3. The colored photosensitive resin composition according to the second aspect of the invention, wherein the epoxy compound (a-1) contains a compound represented by the following formula (1), [Chemical Formula 1] (wherein the plural R1 groups 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 m is an average value, and is 0 to 10 The number of η is an integer of 1 to 4). 4. The colored photosensitive resin composition according to claim 3, wherein the epoxy compound (a-1) is a compound represented by the following formula (2), [Chemical Formula 2] 29 (2) 200819912 (2) (where m is an average value, which means the number of 0 to 10). 5. The colored photosensitive resin composition according to claim 3, wherein the epoxy compound (a-1) has an m system of less than 1. 6. The colored photosensitive resin composition according to claim 1, wherein the polybasic acid anhydride (a-3) is a compound having at least two benzene rings. 7. The colored photosensitive resin composition according to claim 6, wherein the polybasic acid anhydride (a-3) contains at least one of the compounds represented by the following formulas (3) and (4), [Chemical Formula 3] ] \/ 30 200819912 (wherein R2 represents an alkylene group which may have a substituent having 1 to 10 carbon atoms). 8. The colored photosensitive resin composition according to claim 1, wherein the resin has a mass average molecular weight of from 1 Å to 40000. 9. The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (A) contains a monomer having an ethylenically unsaturated group. The colored photosensitive resin composition according to claim 1, wherein the coloring agent (C) is a black pigment. 31 200819912 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: None 4