TW201030459A - Photosensitive resin composition - Google Patents

Abstract

The present invention provides a photosensitive resin composition which possesses an outstanding coating and an outstanding ink repulsive characteristic. The photosensitive resin composition of the present invention contains: photopolymerization compound (A), photopolymerization initiator (B), and fluorine surfactant (C), in which the fluorine surfactant (C) has fluorinated alkenyl group and solvent-philic group on a side chain thereof. As the fluorine surfactant (C), polymer of mass average molecular weight of 5000 - 30000 is preferred; as the fluorinated alkenyl, perfluorinated alkenyl is preferred.

Description

201030459 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition. [Prior Art] A display system such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates in which a pair of electrodes are formed to face each other. Further, a color filter having pixel regions of respective colors of red (R), green (〇), and blue is formed on the inside of the gusset substrate. In order to improve contrast and prevent light leakage, the color filter is usually formed in a matrix of black matrices to divide pixel regions of R, G, and B colors. Conventionally, a color filter is manufactured by first forming a black matrix by a lithography method, and repeatedly coating, exposing, and developing each photosensitive resin composition of each of a ruler, a cymbal, and a sixth color by the black matrix. In each of the regions, the respective color patterns are formed at predetermined positions. In recent years, in order to improve productivity, a method of manufacturing a color light film by an ink jet method has also been explored. In this inkjet method, inks of respective colors of R, G, and b are ejected from the ink ejecting nozzles into respective regions divided by the formed black matrix, and then the accumulated ink is hardened by heat or light. A color calender is produced. However, in the ink jet method, in order to prevent ink generation between adjacent pixel regions, a photosensitive resin composition for forming a black matrix is required, and an anti-solvent for an ink solvent such as water or xylene is required. Sex, the so-called repellency. 3 201030459 Such a photosensitive resin composition having ink repellency, for example, a negative photosensitive resin composition containing an ink repellent agent is disclosed (Patent Document 〇, the ink repellent agent is a polymer having the following polymerization unit) Forming, that is, having at least one of a nitrogen atom substituted with a fluorine atom and having an alkyl group having 2 or less carbon atoms (wherein the above alkyl group includes an etheric oxygen atom), and having an ethylenic double The polymerization unit of the bond. The negative photosensitive resin composition is obtained by the fluorinated alkyl group of the ink repellent to obtain ink repellency. Further, since the ink repellent contains a polymer unit having an ethylenic double bond, light can be utilized. In the case of the invention, the problem of the ink repellent is maintained. [Patent Document 1] International Publication No. 2004/042474 [Problems to be Solved by the Invention] However, the composition of the negative photosensitive resin described in Patent Document 1 Though the ink repellency is excellent, the coating property is problematic. The present inventors have thought of adding a surfactant which is considered to be effective in improving coatability in order to improve coatability. In the development of a photosensitive resin composition in which an ink repellent is substituted with a perfluoroalkyl group-containing fluorine-based surfactant, it has been found that although the coating property is improved, the ink repellent property is problematic. The present invention is based on the above problems. The object of the present invention is to provide a photosensitive resin composition which has excellent coatability and excellent ink repellency. 4 201030459 [Technical means for solving the problem] The inventors have found that it can be specified by using The present invention provides the following, and the present invention provides a photosensitive resin composition containing a photopolymerizable compound (4) and photopolymerization. a photosensitive resin composition of the initiator (8) and the gas-based surfactant (c), wherein the fluorine-based surfactant (c) has a fluorinated alkenyl group and a solvophilic group in the side chain. The photosensitive resin composition of the invention has excellent coatability and excellent ink repellency. Therefore, it is suitably used for forming a frame represented by a black matrix such as a color filter (grid). [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, an embodiment of the present invention will be described. The photosensitive resin composition of the present invention contains a photopolymerizable compound (A) and a photopolymerization initiation. The agent (B) and the fluorine-based surfactant (c) are described below. [Photopolymerizable compound (A)] The photopolymerizable compound (A) is polymerized and hardened by irradiation with light such as ultraviolet rays. The material "polymerizable compound (A) is preferably a resin or a monomer having an ethylenically unsaturated group, more preferably such a combination. The resin having an ethylenically unsaturated group and having ethylene by 201030459 When the monomers of the unsaturated group are combined, the curability is improved and the pattern is easily formed. Further, in the present specification, in the case of a compound having an ethylenically unsaturated group, a mass average molecular weight of 1,000 or more is referred to as "having "Ethylene-unsaturated resin", the mass average molecular weight of less than 1000 is called "single-band with ethylenically unsaturated group" » "Resin with ethylenically unsaturated group" Φ As the resin having an ethylenically unsaturated group, (meth)acrylic acid, transbutanic acid, cis-butane diacid, and anti-butyric acid monodecyl fumarate monoethyl ester , 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, glyceryl (meth) acrylate, (meth) propylene Indoleamine, acrylonitrile, methacrylonitrile, (▼-) methyl acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl acrylate (Methyl) benzyl acrylate, ethylene glycol di(meth) acrylate, diethylene glycol diacrylate, triethylene glycol di(methyl) propylene phthalate, tetraethylene glycol bis ( Methyl) acrylate, butanediol dimethyl acrylate, propylene glycol di(meth) acrylate, trimethylolpropane tri(methyl) acrylate, tetramethyl methacrylate Acetate, pentaerythritol tris(fluorenyl) acrylate, pentaerythritol tetrakis (meth) acrylate, dipentaerythritol penta (methyl) Oligomerization obtained by polymerization of acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol di(meth) acrylate, cardo ep〇xy diacrylate, etc. a polyester (mercapto) acrylate obtained by reacting (meth)acrylic acid with a polyester prepolymer obtained by condensing a polyol with a monobasic acid or a polybasic acid, and a polyol 6 201030459 Poly(meth)acrylic acid amide phthalate obtained by reacting with a compound having two isocyanate groups and then reacting with (meth) propyl hydrazine; making a double-type epoxy resin, bisphenol F type Epoxy resin, bisphenol S type epoxy tree sausage, phenol or cresol novolac type epoxy resin, resol epoxy resin, trisphenol methane epoxy resin, polycarboxylic acid polycondensation water Epoxy resin obtained by reacting an epoxy resin such as glyceride, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin or dihydroxybenzene type epoxy resin with (meth)acrylic acid ( Methyl) acrylate resin or the like. Further, a resin obtained by reacting a polybasic acid anhydride with an epoxy (fluorenyl) acrylate resin can be used. Further, a resin having an ethylenically unsaturated group can be preferably used by further reacting an epoxy compound (al) with a carboxylic acid compound (a2) containing an ethylenically unsaturated group, and a polybasic acid anhydride (a3). The resin obtained by the reaction. <Epoxy compound (al)&gt; Examples of the epoxy compound (al) include a glycidyl ether type, a shrinkage glyceride type, a glycidylamine type, an alicyclic type, a bisphenol A type, and a bisphenol F type. Bisphenol S type, biphenyl type, naphthalene type, first type, phenol novolak type, ortho-type ring-type resin. Among them, a biphenyl type epoxy resin is preferred. The biphenyl type epoxy tree is known to have i or more of the following formulas (the biphenyl skeleton represented by "." and has one or more epoxy groups in the main chain. Also, as an epoxidized anthracene (al)' It is preferred to have two or more epoxy groups. The epoxidized opening (al) may be used singly or in combination of two or more. [Chemical Formula 1] 201030459

In the formula (al-〇, a plurality of Ru independently represent a hydrogen atom, an alkyl group having 1 to U carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and 1 represents an integer of 1 to 4.

The conjugated epoxy tree wax is preferably used in the following formula (Η·.). No: epoxy resin, particularly preferably used in the ring represented by the following formula (al 3) = fat ° by using &lt;; (al_3) epoxy resin, well obtained

Sensitivity and solubility, and clear pixel edge (sharP) &amp; photosensitive resin composition excellent in adhesion. [Chemical Formula 2]

In the formulas (al-2) and (al-3), a plurality of R2a knives independently represent a hydrogen atom, an alkyl group having a concentration of 1 to 12, a phenyl group which may or may have a substituent, and a The integer "q" is the average value.

P is 1 in the range of 0 to 10, preferably 8 201030459. Further, in the biphenyl type epoxy resin, an epoxy resin represented by the following formula (al-4) is preferably used. By using the epoxy resin of the formula (al 4), it is possible to obtain a photosensitive resin composition which is excellent in balance between sensitivity and solubility, and which is excellent in clarity and adhesion of the edge of the pixel. [Chemical Formula 3]

(a 1-4) In the formula (al-4), a plurality of phenyl groups each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a substituent. ^ is an average value, and the number of 0 to 10' is preferably less than 1. <The carboxylic acid compound (a2) containing an ethylenically unsaturated group> • As the acid-reducing compound (a2) containing an ethylenically unsaturated group, it is preferable to contain a reactive group such as a propenyl group or a methyl propyl group in the molecule. A mono-decanoic acid compound having a dilute double bond. Examples of such an ethylenically unsaturated group-containing carboxylic acid compound include acrylic acid, mercaptoacrylic acid, stupid vinyl acrylate cold-mercaptoacrylic acid, cyanocinnamic acid, and cinnamic acid. The carboxylic acid compound (a2) containing the ethylenically unsaturated group may be used singly or in combination of two or more. As a method of reacting the epoxy compound (al) with the ethylenically unsaturated group-containing carboxylic acid compound (a2), a known method can be used. For example, it can be listed as 9 201030459 by the following methods: tertiary amine such as triethylamine or benzylethylamine; gasification of tridecyltrimethylammonium, vaporized tetramethylammonium, vaporized tetraethylammonium, gasification a quaternary ammonium salt such as a triethylammonium group; a catalyst such as a pyridine or a triphenylphosphine, and a reaction temperature of 50 C to 150 C in an organic solvent to make the epoxy compound (ai) and ethylene-containing The unsaturated carboxylic acid compound (a2) is reacted for several hours to several tens of hours. The ratio of the use ratio of the epoxy compound (al) to the carboxylic acid compound ruthenium (a2) containing an ethylenically unsaturated group, and the epoxy equivalent of the epoxy compound (al) and the ethylidene-unsaturated group The ratio of the carboxylic acid equivalent of the acid compound 16 (a2) is usually US&quot;, preferably 1: 〇8 to 1:125, more preferably 1...the crosslinking is improved by setting it as the above-mentioned Fanyuan' The tendency of efficiency is better. <Polyure acid anhydride (a3)> The second-reading anhydride (a3) is an acid anhydride having two or more carboxyl groups and a compound having at least two benzene rings. Examples of the polybasic acid g C a3 ) ' include, for example, a fatty acid such as a skeleton, and two benzene rings represented by the formula (a) and the bond # 〇a3·2) represented by the following formula (a3_1). Smuggled by the base of the machine. [Chemical Formula 4] 10 201030459

In the formula (a3-2), R4a represents a stretchable group having a carbon number which may have a substituent. At least two benzene rings can be introduced into the photopolymerizable compound (A) by using the acid anhydride of the carboxylic acid having two or more mercapto groups. Further, the polybasic acid anhydride (a3) may include other polybasic acid anhydrides in addition to the above-mentioned acid having at least two benzene rings. Examples of the other polybasic acid anhydride include: cis-butanic acid liver, succinic acid liver, sulfhydryl succinic anhydride, o-% phthalic anhydride, tetraphthalic phthalic anhydride, and hexahydrophthalic anhydride. , methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, dimercapto ketone tetraphthalic acid dianhydride, 3-mercaptohexahydrogen Dicarboxylic anhydride, 4-mercaptohexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3- Mercaptotetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride. These polybasic acid anhydrides may be used singly or in combination of two or more. As the method of reacting the epoxy compound (al) with the ethylenically unsaturated group-containing tick acid 11 201030459 compound (a2) and further reacting with the polybasic acid anhydride (a3), a known method can be used. Further, the amount ratio of use, the molar number of OH groups in the reaction product of the epoxy compound (al) and the ethylenically unsaturated group-containing acid-suppressing compound (a2), and the acid liver group of the polyacid liver (a3) The equivalent ratio is usually 1: 1~1 : 〇.1, preferably! : 0 8~i : 〇 2. It is preferable to set it as the above range and to have a moderate tendency to dissolve the developer. _ The acid value of the resin obtained by further reacting the reactant of the epoxy compound (al) with the ethylenically unsaturated group-containing carboxylic acid compound (a2) with the polybasic acid anhydride (a3), based on the resin solid content Preferably, it is l〇mgK〇H/g~150 mgKOH/g′ more preferably 70 mgKOH/g~110 mgKOH/g. By setting the acid value of the resin to 1 〇mgK〇H/g or more, sufficient solubility in the developer can be obtained, and by setting it to 15 〇 mgKOH/g or less, sufficient hardenability can be obtained, and Make the surface good. Further, the mass average molecular weight of the resin is preferably from 1 Torr to 4 Torr, and more preferably from 2,000 to 30,000. By setting the mass average molecular weight to 1000 or more, heat resistance and film strength can be improved, and by setting it to 4 Torr or less, sufficient solubility in the developer can be obtained. Further, as the resin having an ethylenically unsaturated group, a resin having a fluorene structure in a molecule can be preferably used. Since the resin having a ruthenium structure has high heat resistance and chemical resistance, the photopolymerizable compound (A) can be used to improve the heat resistance and chemical resistance of the photosensitive resin composition. For example, a resin represented by the following formula (a4 l) can be preferably used. [Chemical Formula 5] 12 201030459

' COOH

I

HOOC— Y- CO — 〇--x —〇—CO— Z—CO— 0——X—0—CO— Y-COOH

I

COOH _ J 8 (a4-1) In the formula (a4-1), X is a group represented by the following formula (a4-2). [Chemical Formula 6]

Further, in the formula (a4-1), Y is derived from maleic anhydride, succinic anhydride, methylene succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid Removal of a carboxylic acid anhydride group (-CO-0-CO-) in a dicarboxylic anhydride such as an acid anhydride, methyl endomethylenetetrahydrophthalic anhydride, chloro-bromic anhydride, mercaptotetrahydrophthalic anhydride or glutaric anhydride ) the resulting residue. Further, in the formula (a4-1), the Z system is removed from tetracarboxylic dianhydride such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride. Residues obtained from two carboxylic anhydride groups. Further, in the formula (a4-1), s is an integer of 0 to 20. "Monomer having an ethylenically unsaturated group" Among the monomers having an ethylenically unsaturated group, there are a monofunctional monomer and a polyfunctional monomer of 201030459. The monofunctional monomer 'is exemplified by (mercapto) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (methyl) Acrylamide, propoxymercapto (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyl Base (mercapto) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, methylene succinic acid, methylene succinic anhydride, methyl sulfhydryl Succinic acid, methyl cis-butanic acid, butyric acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide, methyl methacrylate , ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl ketone (meth)acrylate, Methyl) acrylate 2- propyl ester, (meth) acrylic acid 2 _ butyl vinegar, (mercapto) propionic acid 2-phenoxy-2- propyl vinegar, phthalic acid 2 _ ( Methyl) propyl methoxy-2-hydroxypropyl ester, single (meth)acrylic acid glyceride, tetrahydroanthracene (meth)acrylate, dimethylamine (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid 2,2,2·3 Fluorine ethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid half-ester of phthalic acid derivative, etc., such monofunctional monomers may be used alone or 2 Use in combination of the above. On the other hand, 'as a polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol II (Meth) acrylate, polypropylene glycol di(meth) acrylate, butanediol di(meth) acrylate, neopentyl glycol bis(hanyl) acrylate, 1,6-hexanediol di(a) Acrylate, trimethylolpropane tri(meth)acrylate, di(meth)acrylic acid glyceride, pentaerythritol tripropylene 201030459 acid ester, pentaerythritol tetraacrylate, diquaternic pentaerythritol pentaacrylate, dipentaerythritol Acrylic vinegar, pentaerythritol di(▼) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(methyl) propyl acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(indenyl) acrylate Ester, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propyl decyloxypolyethoxyphenyl ) propylene, (methyl)propionic acid 2-hydroxy-3-(methyl) Alkyloxypropyl acrylate, ethylene glycol diglycidyl ether bis(曱φ) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, phthalic acid diglycidyl Ester di(mercapto) acrylate, glyceryl triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, (meth) acrylate urethane (ie 'toluene diisocyanate), trimethyl hexa a reaction product of mercapto diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate, methylene bis(meth) acrylamide, (meth) acrylamide, methylene ether, A polyfunctional monomer such as a condensate of a polyhydric alcohol and N-methylol (meth) acrylamide, or a polyfunctional monomer such as tripropylene acetal may be used Φ alone or in combination of two or more. . The content of the monomer having an ethylenically unsaturated group is preferably from 5 to 5 % by mass, more preferably from 〇 to 40% by mass, based on the solid content of the photosensitive resin composition. By setting it as the said range, it is easy to acquire the balance of sensitivity, developability, and analytical property, and it is preferable. The content of the photopolymerizable compound (Α) is preferably from 5 to 50% by mass, more preferably from 1 to 4% by mass, based on the solid content of the photosensitive resin composition. By setting it as the said range, it is easy to acquire the balance of sensitivity, developability, and an analytical property, and it is preferable. 15 201030459 [Photopolymerization initiator (B)] As a photopolymerization initiator (B) ', 丨-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-phenyl phenylpropane-1- Ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropan-1-yl, 1-(4-didecylphenyl)-2-yl-2-methylpropan-1-one, 2,2-dimethoxy -1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)anthracene, 2-methyl-1-[4-(methylthio)phenyl]-2-? 2-methyl -1 - [4-(methy lthio)phenyl]-2-morpholino propane-1-one), 2-benzyl-2-dimethylamino-1- (4-?-ylphenyl)·butan-1-one, ethyl ketone-1·[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazolyl-3-yl] -1-(o-Ethyl), 2,4,6-trimercaptobenzoyldiphenyl oxide scale, 4-phenylhydrazin-4·-mercaptodimethyl sulfide, 4-dioxene Aminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-diaminoamine butyl citrate, 4-dimethylamino-2- Ethylhexylbenzoic acid, 4-dimethylamino 2-episopentyl bromide Acid, benzyl-fluorenyl-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, o-benzene Methyl mercaptobenzoate, 2,4-diethyl thioxanthone, 2-oxythioxanthone, 2,4-dimethylthioxanthone, 1-aluminum-4-propoxythioxanthone, Thiophene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-mercaptothioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, octamethylguanidine, 1,2 -benzopyrene, 2,3-diphenylfluorene, azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole (2-mercaptobenzoxazole), 2-mercaptobenzothiazole, 2·(o-phenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, dibenzophenone, 2_gas Dibenzophenone, bis-dimethylaminobenzophenone, 4,4 bisdiethylamine 201030459 benzophenone, 4,4'-dibenzobenzophenone, 3,3_two Methyl-4 methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, phenelzine, 2 , 2-2-B Benzo acetophenone, p-dimethylacetophenone p-dimethylaminopropiophenone, dioxetane, tri-o-acetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, For t-butyl tri-o-acetophenone, p-tert-butyl diacetophenone, α,α_di- gas _4-phenoxy acetophenone, thioxanthene, 2-methyl thioxanthone, 2-isopropyl thioxanthene, dibenzocycloheptanone, amyl 4-dimethylaminobenzoate, 9-phenyl acridine, 17-bis-(9-acridinyl) heptane, 15 Bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytdazine, 2,4,6_three (three gas Triazine, 2 methyl-4,6-bis(trichloromethyl)-s-triazine, 2[2_(5-methylfuran-2-yl)vinyl M,6-bis(trimethylmethyl) )_s-triazine, 2_[2(bate-2-yl)vinyl]-4,6-bis(dimethylmethyl)-s-triazine, hydrazine [2_(4 diethylamino-2-methylbenzene) Vinyl]-4,6-bis(trimethylmethyl)_s-triazine, 2_[2(3,4 dimethoxyphenyl)vinyl]-4,6_bis (three gases Methyl)-s-triazine, Μ#methoxyphenyl)-4,6-bis(trichloromethyls-triazine, 2(1)ethoxybenzene Alkenyl) 4,6·bis(dimethylmethyl)-homogeneous, Qin, 2_(4_n-butoxyphenyl)_4,6-bis (trioxanyl-triazine, 2,4-bis- Trichlorof-yl-6-(3bromo-4-yloxy)phenyl--tris-methyl 2'4-bis-dimethyl-6-(2-bromo-4-methoxy)phenyl- Triazine, 2,4-bis-trismethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trismethyl-6- (2-Bromo-4·decyloxy)styrylphenyl-s-triazine or the like. In terms of sensitivity, it is particularly preferable to use a lanthanide photopolymerization initiator. These photopolymerization initiators may be used singly or in combination of two or more, such that 201030459 is 0 with respect to the solid content of the photosensitive resin composition, and the photopolymerization initiator (B) is preferably 〇.5 to 30. quality. /. 'Better is the range of quality 0/〇. When it is in the above range, sufficient heat resistance and chemical resistance can be obtained, and film formability can be improved, and photohardening failure can be suppressed. [Fluorine-based surfactant (C)] φ The fluorine-based surfactant (C)' contained in the photosensitive resin composition of the present invention is a polymer having a fluorinated alkenyl group and a solvophilic group in a side chain. The fluorine-based surfactant (C) has a high liquid repellency as compared with a fluorinated alkyl group by containing a fluorinated alkenyl group. The fluorinated alkyl group preferably has 2 to 20 carbon atoms, preferably a fluorinated alkenyl group having 6 to 10 carbon atoms (including a trans form and a cis form). Specific examples thereof include perfluoro-2-hexyl-2-yl, all-1-2-hept-2-yl, perfluoro-(2-,3-, or 4-)octene-2 -based, perfluoro-(2-,3-, or 4-)nonen-2-yl, perfluoro-(2-,3-, _ or 4-)nonen-2-yl, perfluoro-2 -ethyl-1-buten-1-yl, perfluoro-4-methyl-3-isopropyl-2-pentan-2-yl, perfluoro(2-isopropyl-1,3-di Methyl-1-butenyl), perfluoro(1-ethyl-2-methylindolyl), perfluoro-2-methyl-2-penten-3-yl, and the like. Among these, it is preferably a branched one. By being branched, liquid repellency can be improved. Further, the ratio of the fluorination is preferably 25% or more of the hydrogen atom in the fluorocarbon, and is preferably replaced by a fluorine atom, preferably 50°/. The above substituted by a fluorine atom is particularly preferably a perfluoroalkenyl group in which all hydrogen atoms are replaced by a fluorine atom. Among such fluorinated alkenyl groups, it is particularly preferred to be represented by the following (cl-Ι) or (cl-2) 201030459. [Chemical Formula 7]

(C1-2)

As a single enthalpy of the fluorinated alkenyl group in this sentence, the singularity of (Μ) is also referred to as "the second type of surfactant (C1) J). By fluoropolymer, There may be b; a kind of J Dan directional ink repellency having a monomer (ci) as a repeating unit. [Chemical Formula 8]

RlC^V〇XR^Rf 〇 (C1-3) In the formula (Cl-3), Rlc represents a hydrogen atom or a methyl group, and Rf represents the above alkenyl group. R represents an alkylene group having a carbon number of 丨~1〇, which may be linear or branched. It may be a solvophilic group, and a conventionally known nonionic surfactant may be mentioned. An ether bond, an ester bond or a carbonyl interrupted alkyl group is preferred, and a polyepoxyalkylene group (p〇lyalkylene〇xy) (polyepoxyalkylene group, polypropylene oxide group, polycyclic ring) Oxybutylene) is preferred. 201030459 The fluorine-based surfactant (c) can be obtained at least by polymerizing the above monomer having a fluorinated alkenyl group and the above monomer having a solvophilic group. The monomer having a solvophilic group is preferably a monomer having an ethylenically unsaturated group and a structure represented by the following formula (c2-1) (hereinafter also referred to as "monomer (c2)"). (C2-1) The monomer (c2) preferably has an ethylenically unsaturated group and a structure represented by the following formula (C2-2). [Chemical Formula 10]

(C2-2)

It can be branched. Wherein ' is preferably an alkyl group having a carbon number of 3, most preferably a methyl group. Examples of the substituent include a carboxyl group, a hydroxyl group, and a carbon number of 丨 to 60: an alkyl group such as an alkoxy group, and an integer of 1 or more, more preferably an integer of 1 to 12. Examples of such a monomer (c2)' include a compound represented by the following formula (c2_3). These monomers (c2) may be used singly or in combination of two or more kinds of 201030459. [Chemical Formula 11] RSc 〇-L.R4c R3e CH2=C-C-〇

II ο (c2-3) In the formula (c2-3), R5c represents a hydrogen atom or a fluorenyl group. The meanings of r3c, r4c, &gt; are the same as those of the above formulae (c2-l) and (c2-2). β &quot; • &amp; is a fluorinated alkenyl group and a solvophilic group in the surfactant (C). Preferably, the molar ratio of the monomer having a Dunkenyl group (c) to the monomer having the solvophilic group (c2) is preferably 99 to 5: 5, preferably ! : 99~25: 75, best for 5: 95~25: 75. Among these, it is preferable to use a fluorine-based surfactant obtained by polymerizing a monomer (U) in which Rf is a perfluoro group in the above formula (7)-3) and the above monomer (c2), and as a specific example thereof, List: Ftergent 73〇fl (Rf in the above ® 弋(cl-3) is an acrylic monomer represented by the above formula (cl-1): C has an epoxy group in the formula (c2-3) Dilute acid monomer = 3: 97 (mole ratio), Ftergent 710FL (Rf in the above formula (cl_3) is an acrylic acid shown by the above formula (Cl 1): Ethylene B in the above formula () Acrylic monomer of fluorenyl group = 9: 91 (mole ratio), Ftergent 703FL (In the above formula (cl-3), Rf is an acrylic monomer represented by the above formula (cl-1): the above formula (C2- 3) an oxiranyl group-containing acrylic monomer (cl) 2: 75 (mole ratio) (both manufactured by NEOS Co., Ltd.). The fluorine-based surfactant (C) may be any of a random polymer, a block polymer 21 201030459, and a graft polymer, but a graft polymer is preferred. By providing the graft polymer ', the compatibility with the photopolymerizable compound (a) can be maintained, and the coatability can be improved. Further, in the case of a graft polymer, even if the content is increased, the occurrence of white turbidity is less. The fluorine-based surfactant (c) preferably has a mass average molecular weight of from 5,000 to 30,000, preferably from 1 to 2 Torr. The content of the fluorine-based surfactant (c) is preferably from ITO to 20,000 ppm by mass based on the photopolymerizable compound (A), preferably from 2 to 8 Å. . Even if it is added in a small amount as in the above range, a photosensitive resin layer excellent in ink repellency can be obtained. Further, the photosensitive resin composition of the present invention may contain other conventionally known surfactants within a range not impairing the effects of the present invention. [Colorant (D)] The photosensitive resin composition of the present invention may further contain a colorant. As the ruthenium colorant (D), a light-shielding agent such as carbon black or titanium black can be mentioned. Also, you can use

Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr,

Inorganic pigments such as various metal oxides, composite oxides, metal sulfides, metal sulfates, or metal carbonates such as Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, and ai As the black, a known carbon black such as channel black, furnace black, hot carbon black, or lamp black can be used. In particular, the groove black can be preferably used because it has excellent light blocking properties. Further, a resin-coated carbon black can also be used. Specific examples thereof include: carbon black and a resin reactive with a carboxyl group, a hydroxyl group, or a carbonyl group present on the surface of the carbon black, and a resin-coated carbon black obtained by heating at 50 ° C 22 201030459 to 38 (TC; Or a resin-coated carbon black obtained by dispersing an ethylenic monomer in a water-organic solvent mixed system or a water surfactant mixed system in the presence of a polymerization initiator to carry out radical polymerization or radical copolymerization. Since the resin-coated carbon black has low conductivity as compared with the carbon black which is not coated with the resin, when used as a color filter such as a liquid crystal display, it is possible to form less leakage and high reliability. Low-power consumption display φ As a coloring agent, an organic pigment can be added to the above inorganic pigment as an auxiliary pigment. The organic pigment can be obtained by appropriately adding an organic pigment which exhibits a complementary color of an inorganic pigment to obtain the following effects. Reddish black. Therefore, by adding an organic pigment that exhibits a red complementary color, that is, a blue color, as an auxiliary pigment in carbon black, the red color of carbon black can be eliminated, thereby A better black color is present. The amount of the organic pigment used is preferably in the range of 10 to 80% by mass, more preferably in the range of 20 to 60% by mass, particularly preferably 20%, based on the total of the inorganic pigment and the organic pigment. In the range of 40% by mass, as the inorganic pigment and the organic pigment, a solution obtained by dispersing a pigment at a suitable concentration with a dispersing agent can be used. For example, as the inorganic pigment, a carbon dispersion CF Black manufactured by Yuki Co., Ltd. can be cited. (containing carbon with a concentration of 20%), carbon black CF Black (including 24% high-resistance carbon) manufactured by Yuki Co., Ltd., and titanium black dispersion CF Black (20% black titanium) manufactured by Yuki Co., Ltd. In addition, as the organic pigment, for example, a blue pigment dispersion CF Blue (containing 20% of a blue pigment) manufactured by Yuki Co., Ltd., and a purple pigment dispersion made by Yuki Co., Ltd. (containing 10%) Further, as the dispersing agent, 23 201030459 is preferably used: a polyethyleneimine type, a urethane resin type, or an acrylic resin type polymer dispersing agent. In the solid content of the composition, the content of the coloring agent (D) is preferably from 10 to 70% by mass. By setting the content to 70% by mass or less, photohardening failure can be suppressed, and the content is made 10% by mass. In the above, a sufficient light-shielding property can be obtained. When a photosensitive resin composition of the present invention is used as a black matrix, the concentration of the colorant is preferably adjusted to an OD per 1 #ιη film thickness. The (Optical Density, Optical Density) value is 1.5 or more. When the 〇D value of ι 5 or more per 1 em film thickness is used for the black matrix of the liquid crystal display, sufficient contrast can be obtained.

The photosensitive resin composition of the present invention preferably contains a solvent. Examples of the solvent include ethylene glycol monoterpene, ethyl monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether diethylene glycol methyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol mono-n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol single shout, propylene glycol mono-resonance, propylene glycol mono-n-propyl propene, propylene glycol mono-n-butyl bromide Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly) alkanediol monoalkyl ether; ethylene glycol monomethyl Ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. 24 201030459 Alkanediol monoalkyl ether acetates; diethylene glycol dimethyl ether diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydro anthracene and other ethers; methyl ethyl ketone, a ketone such as cyclohexamine, 2-heptanone or 3-heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethoxyacetate ethyl acetate ethyl acetate, 2-hydroxy-3-methylbutyrate decyl acetate, acetic acid 3 methoxybutyl ester, acetic acid 3_ #methyl_3_methylmercaptobutyl ester, propionic acid 3 · Mercapto-3-hydroxybutyl acrylate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate Ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, decyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate Other esters such as ethyl ester and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Ν-methyl" piroxime, ν, Ν-dimercaptoamine, ν, Ν- The emulsifiable amines such as dimethylacetamide, etc., may be used singly or in combination of two or more kinds thereof. The content of the solvent (S) is relatively larger than 100 parts by mass of the solid content of the photosensitive resin composition. Good for 5〇~5〇〇 parts by mass. [Others In the photosensitive resin composition of the present invention, an additive may be contained as needed. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, and a dispersion. Agent, dispersing aid, filler, adhesion promoter, antioxidant, ultraviolet absorber, anti-agglomeration 25 201030459, etc. [Preparation method of photosensitive resin composition] The photosensitive resin composition of the present invention can be used The above-mentioned components are all obtained by mixing with a stirrer. In order to make the obtained mixture uniform, it can be filtered using a filter. φ [Application example of the photosensitive resin composition of the present invention] The photosensitive resin composition of the invention is suitably used for forming a frame (lattice-like structure) represented by a black matrix of a color light-passing sheet, for example, because of excellent coating properties and excellent ink repellency. Here, as one of the application examples, a method of producing a color filter using the photosensitive resin composition of the present invention will be described below. [Manufacturing Method of Color Filter] First, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or the like, or a rotator A non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is applied to the substrate on the photosensitive resin composition of the present invention. As the substrate, a substrate having light transmittance is used. Then, the applied photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited. For example, any of the following methods can be used: (1) using a hot plate at 80 ° C to 120 °. (:, 26 201030459 is preferably a method of placing 9 hours to TC~·c at a temperature of 6Q~i 2q seconds to the shirt for several hours to several '' (3) in a warm air heater or an infrared heater A method of removing the solvent for several tens of minutes to several hours. Then, the coating film is irradiated with an active energy ray such as an ultraviolet ray or a molecular laser light through a negative mask to perform partial exposure. The amount is, for example, preferably about 30 to 2000 mJ/cm 2 depending on the photosensitive resin composition.

Then, the exposed film is developed with a developing solution to form a pattern of a desired shape. The development method is not particularly limited, and for example, a dipping method, a spray method, or the like can be used. As a developing solution, monoethanolamine is mentioned. An organic developing solution such as ethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt. Then, the developed pattern was post-bake at a temperature of about 200 art. At this time, it is preferable to perform full exposure of the formed pattern. By the above operation, a black matrix having a predetermined pattern shape can be formed. Then, the inks of the respective colors of R, G, and B are ejected from the ink ejecting nozzles into the respective regions divided by the black matrix, and the accumulated ink is hardened by heat or light. Thereby, a color filter can be manufactured. [Examples] Hereinafter, the present invention will be described in detail with reference to examples. Further, the present invention is not limited by any of the following embodiments. <Example 1> The photopolymerizable compound (A) used the following resin (A-1) and 27 201030459 as the monomer (A-2) dipentaerythritol hexaacrylate (DPHA). The synthesis method of the resin (A-1) is as follows. [Synthesis of Resin (A-1)] The synthesis method of the resin (A-1) is as follows. Air was blown at a rate of 25 ml/min on one side at 90 ° C to 100 C to 235 g of bisphenol quinone type epoxy resin (epoxy equivalent of 235 ), 110 mg of tetramethylammonium chloride, 1 2 mg of 2,6-di-t-butyl-4-methylphenol and 72.0 g of acrylic acid were heated and dissolved, and then slowly heated to 12 ° C. Meanwhile, the acid value was measured, and heating and stirring were continued for about 12 hours until the acid value was less than 1.0 mgKOH/g. Then, it was cooled to room temperature to obtain a colorless transparent and solid bisphenol type epoxy acrylate. Then, after adding 3 50 g of propylene glycol monoterpene ether acetate (PGMEA) to the above-mentioned bisphenolphthalein type epoxy acrylate obtained at 307.0 g, 80.5 g of benzophenone tetradecanoic acid was dissolved. The anhydride and 1 g of tetraethylammonium bromide were mixed and reacted at 110 ° C to 115 ° C for 4 hours. After confirming the loss of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin (A-1). Further, the disappearance of the acid anhydride group was confirmed by infrared (IR) spectroscopy. The obtained resin (A-1) was measured by gel permeation chromatograph (GPC) to have a mass average molecular weight of 5,000 and an acid value of 80 mgKOH/g. The resin (A-1) was acetic acid. -3-methoxybutyl ester was adjusted to have a solid content concentration of 55 mass%. As the photopolymerization initiator (B), CGI242 (B-1, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used. 28 201030459 The surfactant (C) is Ftergent 710FL (Cl, (the above formula (cl-3) wherein Rf is an acrylic monomer represented by the above formula (dd): the above formula (c2-3) has epoxy B Alkyl acrylic monomer = 9: 91 (mole ratio), mass average molecular weight is 20000). Colorant (D) is made of black pigment (D-1, manufactured by Royal Color Co., Ltd. 'CF Black: carbon black is 25 % by mass, solvent: 3-methoxybutyl acetate) φ Solvent (S) is a mixed solvent of 3 曱 oxybutyl ester: cyclohexanone = 6 〇: 4 〇 (mass ratio) (S-1) The components and the solvent were mixed to have a solid content concentration of 22% by mass. The mixture was mixed for 2 hours with a stirrer, and then filtered by a membrane filter. The photosensitive resin composition was prepared. The blending amounts are shown in Table 1. <Examples 2 and 3, Comparative Examples 1 and 2> 感光 A photosensitive resin composition was prepared by changing the composition described in Table 1 below. The resin (A_3) in Table 1 The synthesis method is as follows: [Synthesis of Resin (A-3)] Mixing 400 g of EPIKOTE YX4000H (Japan Epoxy Resin) Manufactured by the company, epoxide equivalent: 192), 4 g of triphenylphosphine, 153 g of acrylic acid, 600 g of 3-methoxybutyl ester, and 90 to 100. (: The reaction is carried out. Thereafter, as a polybasic anhydride Further, 40 g of tetrahydrophthalic anhydride and 3 60 g of biphenyltetracarboxylic dianhydride were added to further react, thereby obtaining a resin (A-3) having a biphenyl skeleton. This resin (A-3) The mass measured by GPC was 29, 2010, and the average molecular weight was 7,000, and the acid value was 90 mg K 〇 H / ge. Further, the resin (A") was adjusted to a solid content concentration of 5 〇 mass% with 3-methoxy butyl acrylate. In addition, the surfactant (c_2) in Table 1 is KL 6〇〇 (manufactured by Kyoeisha Chemical Co., Ltd., a fluorine-based surfactant having a polymer containing (meth) acryl acid total octyl vinegar) ), surfactant () is BYK-310 (manufactured by BYK Chemical Co., Ltd., lanthanide surfactant)0

<Evaluation> The photosensitive property prepared in 2 was dried at 90 ° C for 2 minutes, and then the above Examples 1 to 3 and Comparative Example 1 to the resin composition were respectively applied onto a glass substrate via a negative image mask. A photosensitive layer having a film thickness of about 2/m. The photosensitive layer was selectively irradiated with ultraviolet light at an exposure amount of 200 mJ/cm2, and a solution of N-a3K (manufactured by Tokyo Ohka Kogyo Co., Ltd.): pure water = i: 25 was used as a developing solution at 25. (: spray development for 60 seconds, thereby forming a round case. Then, the formed pattern was subjected to post-baking for 3 minutes at 220 C to thereby form a lattice-like black matrix pattern having a line width of 20. Then, for two Ethylene glycol monobutyl ether acetate (BDGAC), diethylene glycol monoethyl ether acetate (EDGAC), 1,3, butanediol diacetate (i, 3_bgda), propylene glycol monomethyl ether (PM) And the pure water' was measured for the contact angle of the solvent formed on the pattern. The results are shown in Table 1. 30 201030459 [Table i] Ingredient Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Resin A-1 A -2 A-3 A-1 A-1 (addition amount: mass%) (6) (12) (6) (6) (6) Monomer A-2 A-2 A-2 A-2 A-2 (Addition amount: mass%) (4) (7) (4) (4) (4) Photopolymerization initiator B-1 B-1 B-1 B-1 B-1 (addition amount··% by mass) (2) (3) (2) (2) (2) Surfactant C-1 C-1 C-1 C-2 C-3 (addition: mass ppm) (4000) (4000) (4000) ( 10000) (10000) Colorant D-1 No D-1 D-1 D-1 (addition amount: mass ° / 〇) (10) (〇) (10) (10) (10) Solvent S-1 S- 1 S-1 S-1 S-1 (addition amount: mass%) (78) (78) (7 8) (78) (78) Contact angle (degrees) BDGAC 54 53 54 34 31 EDGAC 53 53 54 34 30 1,3-BGDA 53 52 54 33 30 PM 45 44 46 28 27 Pure water 110 110 110 99 97 1 It is understood that the fluorinated alkenyl group and the solvophilic property are used in the side chain by using a surfactant containing a perfluoroalkyl group (Comparative Example 1) or a fluorene-based surfactant (Comparative Example 2). Based on the fluorine-based surfactant (real φ Examples 1 to 3), excellent liquid repellency can be obtained. [Simple description of the diagram] No [Main component symbol description] No 31

Claims (1)

201030459 VII. Patent application scope: 1. A photosensitive resin composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a photosensitive resin composition of a fluorine-based surfactant, The gas phase surfactant (C) has a fluorinated alkenyl group and a solvophilic group in the side chain. The photosensitive resin composition according to the first aspect of the invention, wherein the fluorine-based surfactant (C) is a polymer having a mass average molecular weight of from 5,000 to 30,000. 3. The photosensitive resin composition according to claim 1, wherein the fluorinated alkenyl group is a perfluoroalkenyl group. 4* The photosensitive resin composition according to Item 1, wherein the fluorinated alkenyl group is branched. 5. The photosensitive resin composition as described in claim 1, wherein the fluorinated alkenyl group is represented by the following formula (cl-1) or (cl-2). [Chemical Formula 1] 32 201030459 6. The photosensitive resin composition according to claim 1, wherein the molar ratio of the fluorinated alkenyl group to the solvophilic group is 1:99 to 50: 50 0 7. The photosensitive resin composition according to the above aspect, wherein the content of the fluorine-based surfactant (C) relative to the photopolymerizable compound (A) is from 1,000 to 20,000 ppm by mass. 8. The photosensitive resin composition described in the first aspect of the patent application, wherein the ® further contains a coloring agent (D). 33 201030459 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: