TWI309339B - Photosensitive composition - Google Patents

Description

130933

IX. Description of the invention: [Technical field to which the invention pertains] 筻fr"Biao Qiao:® Case Bamboo Year, Monthly Revision The present invention relates to a photosensitive composition suitable for forming a black matrix used for displays such as liquid crystal panels ( Black matrix) and / or color filter. [Prior Art] The liquid crystal panel, such as the TN mode and the STN mode, has a black matrix for emphasizing image contrast, or RGB usually composed of red (8), green (G), and blue (B) colors. Color filter for the colored layer. The color matrix or the colored layer is formed by coating a photosensitive composition in which black or various colorants are dispersed on a base plate, and after drying, repeating the exposure and the coating step on the formed coating film. (4) A pattern of demand. When the photosensitive composition is applied to a substrate, in recent years, the method 1 of the slit nozzle has been gradually used, and this method causes a problem that agglomerates of foreign matter are generated on the substrate. Such a foreign matter is sufficient to be a defect of a black matrix and/or a color calender sheet, and becomes a defective product. In the use of a photosensitive composition of a black pigment such as carbon black, the foreign matter becomes a significant problem: ', in order to solve this problem, the patent The document 1 discloses that a resin composition is a mixed solvent having a specific physical property in a specific relationship, but the problem of foreign matter cannot be completely solved. [Patent Document 1] JP-A-2004-246340 SUMMARY OF THE INVENTION The present invention (4) can suppress the occurrence of foreign matter when the photosensitive composition 5 1309339 is applied to a substrate at the above-mentioned problem. Humanity: The photosensitive steep composition is characterized by (4) a colorant, (b) a photopolymerization initiator, and (d) a photosensitive combination of a solvent, and a dialkyl diol monoalkyl group (IV) (4) Solvent. The above-mentioned dialkyl diol monoalkyl ether R - 〇 - CnH2n - 〇 - CnH2n - 〇 H (wherein R1 is a linear number of carbon number 8 and an integer of 2 to 5 of the square ' π system) It is better. By the following formula (1) (1) alkyl or branched or cyclic

[Effects of the Invention] When the photosensitive composition is applied to a substrate according to the above-described structure, in particular, when the coating is applied by a slit nozzle coating method, generation of foreign matter can be suppressed, and a high-quality black matrix and color can be provided. The light-passing film can provide a high-quality liquid crystal panel. [Embodiment] The photosensitive composition of the present invention contains a (&) coloring agent, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and (d) a solvent photosensitive composition containing a dipth The alkyl glycol monoalkyl ether is used as the solvent (d). The above (a) coloring agent is, for example, a coloring index (CI; issued by The Society of Dyers and Colourists), which is a compound of a pigment, and specifically Compound of index (CI) number. c. I · Pigment Yellow-1 (hereinafter, "c _ I. Pigment Yellow" is the same, only 呓 号 6 1309339), 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 , 137 , 138 , 139 , 147 , 148 , 150 丨 , 151 , 152 , 153 , 154 , 155 , 156 ' 166 ' 167 ' 168 , 175, 180, 185; (:.1. Pigment Orange - 1 (hereinafter, Γ CI Pigment Dial" is the same, only the record number), 5, 13, 14, 16, 17, 7, 24, 34, 36, 38 ' 40 ' 43 ' 46 ' 49 ' 51 ' 55, 59 '61' 63, 64, 71, 73 ; CI Pigment Violet - 1 (hereinafter, Γ CI Pigment Violet is the same, only the record number), 19, 23, 29, 30, 32, 36, 37, 38;, 39, 40, 50; CI Pigment Red - 1 (below, Γ CI Pigment Red) is the same, only the record number), 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 3 1, 32, 37, 38 '40, 41, 42, 48: 1, 48: 2, 48: :3, 48: 4 ' 49 : 1, 49 : 2, 50 : 1,

52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63:2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102 > 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172 , 174, 175, 176, 177, 178, 179, 180, 185, 187, 188 ' 190 ' 192 , 193 , 194 , 202 , 206 , 207 , 208 , 209 , 215 , 216 , 217 , 220 , 223 , 224 , 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; CI Pigment Blue·1 (hereinafter, "CI Pigment Blue" is the same, only the record number

1309339 code), 2, 15, 15: 3, 15: 4, 15: 6, 16' 22, 60, 64, CI Pigment Green-7, CI Pigment Green-3 6, CI Pigment Green-3 7; CI Pigment -23-23, CI Pigment Building-25, CI Pigment Building-26, Pigment Brown-2 8; CI Pigment Black-1, CI Pigment Black-7. (a) The amount of the coloring agent to be added is appropriately changed in accordance with the target color tone for (b) the photopolymerizable compound (or the polymer binder and the photopolymer) and (the total amount of the photopolymerization initiator) Usually, it is preferably added in the range of 5 parts by weight, more preferably in the range of about 1 〇 to 200 parts by weight. Further, when a black matrix is formed, an opacifier is used as a coloring agent. When the light agent is used as a light shielding layer, it has sufficient light shielding. The rate is not particularly limited to, for example, a black pigment. The black pigment may be carbon black, titanium black, or diphenyl black, and the colorant may be added in order to adjust the color tone to achieve higher resistance. Further, in general, in order to maintain a black matrix (formed by applying a light-shielding agent as a coloring photosensitive composition), the light-shielding ratio is preferably 1.5 or more, more preferably 3.0 or more, and more preferably 4.0 or more. 100 parts by weight of (b) a photopolymerizable compound (or a polymer binder and a conjugate monomer) and (c) a photopolymerization initiator, and a masking agent is added to the photosensitive composition. The amount of the agent is from 20 to 150 parts, preferably from 25 to 100 parts by weight, and from 30 to 80 parts by weight, more preferably 20 parts by weight or more, to provide a matrix having sufficient light blocking properties. The above range is 150 parts by weight or less, which can prevent 66; CI, phase single ~ 250 circumference is the occlusion, and naphthalene embedded in the L OD light distribution of the agent is good. Black hardening 8 1309339

F] 8

Bad, forming a good black matrix. Concentrate, diacetic acid dilute 2-ene \ tetrapropyl methene, and the above (a) coloring agent can be used as a dispersing agent to obtain a suitable degree (for example, 10 to 20%), and other components. mixing. The dispersion is not particularly limited. For example, a poly(ethyleneimine)-based or urethane resin-based acrylic resin-based polymer dispersant can be used.

The above (b) photopolymerizable compound is produced by irradiation of light such as ultraviolet light to cause polymerization and hardening. The photopolymerizable compound is preferably a compound having an ethylenic double bond, specifically acrylic acid, mercapto methic acid fumaric acid, maleic acid, transbutylammonium dicarboxylate, and methacrylic acid monoethyl bromide Ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate monodecyl ether acrylate, ethylene glycol monodecyl ether methacrylate, ethylene glycol ethyl ether acrylate, ethylene Alcohol monoethyl ether methacrylate, glycerin acrylate, glycerol methyl acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, decyl acrylate, methyl propionate Methyl ester, ethyl acrylate, ethyl methacrylate, isobutyl acrylate isobutyl methacrylate, 2-ethylhexyl acrylate, ethyl hexyl methacrylate, benzyl acrylate, benzyl methacrylate Ethylene glycol dipropionate, ethylene glycol dimercapto acrylate, diethylene glycol diacrylate triethylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol Acrylate, tetraethylene glycol didecyl acrylate, butanol dimercapto acrylate Propylene glycol diacrylate, propylene glycol didecyl enoate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetrahydrocarbyl propane tetraacrylate, Neopentyl alcohol triacrylate, neopentyl alcohol tridecyl propyl 9 1309339

Acid ester, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexapropylene acid Single vinegar (DPHA), dipentaerythritol hexamethylene acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, Cardo epoxy diacrylate a poly(meth)acrylate obtained by reacting (meth)acrylic acid with a polyester prepolymer (condensed from a polyhydric alcohol with a unit acid or a polybasic acid), and a polyhydric alcohol group. Poly(meth)acrylic acid urethane obtained by reacting with a compound having two isocyanate groups, which is obtained by reacting with (meth)acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, double Phenol S type epoxy resin, phenol or nonylphenol phenolic epoxy resin, resol type epoxy resin, trisphenol decane type epoxy resin, polyglycol polyacrylate, polypolyol poly ring Epoxy acrylate, aliphatic or cycloaliphatic epoxy resin, amine based epoxy resin, dihydroxybenzene type epoxy resin, etc. An epoxy (f-based) acrylate resin obtained by reacting with (meth)acrylic acid. Further, a resin produced by reacting the above epoxy (meth) acrylate with a polybasic acid anhydride can also be applied. Further, a compound represented by the formula (1) can be used as a photopolymerizable compound. The compound of the formula (I) is a preferred compound because of its high photocurability. 10 1309339 [Chemical Formula 1]

COOH

CO HOOC-Y-CO——Ο—X-0

Z-CO-O——X-O-CO-Y-COOH

I COOH J n

Here, m is an integer of 1 to 20. Further, X of the compound of the formula (I) is preferably a group represented by the formula (II). [Chemical Formula 2]

Lithic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro ugly anhydride, hexahydro phthalic anhydride, methyl and fluorenyl tetrahydrophthalic anhydride, gas bridge anhydride, mercapto tetrahydrophthalic anhydride, glutaric anhydride, etc. The residue after removal of the carboxylic anhydride group (-C 0-0-CO-). Further, the oxime of the compound represented by the formula (I) is, for example, tetracarboxylic acid such as pyromic anhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride or biphenyl ether tetracarboxylic dianhydride. The residue after removal of the two carboxylic anhydride groups in the dianhydride. These photopolymerizable compounds may be used alone or in combination of two or more kinds of 11 1309339. The photopolymerizable compound in which the molecule itself can be polymerized is listed above, and in the present invention, (b-1) polymer binder and (b-2) photopolymerizable monomer may be contained in (b) photopolymerizable compound. a mixture. The above (b-1) polymer binder is preferably a binder which can be developed by alkali, from the viewpoint of easiness of development.

Specifically, for example, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid, decyl acrylate, decyl decanoate, ethyl propionate, ethyl mercaptopropionate, 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, methacrylic acid Copolymer of benzyl ester, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile, etc. And phenol resol type epoxy acrylate polymer, phenol resol type epoxy methacrylate polymer, indophenol phenolic epoxy acrylate polymer, cresol resol epoxide A resin such as a acrylate polymer, a bisphenol A epoxy acrylate polymer, or a bisphenol S epoxy acrylate polymer. Since the above-mentioned resin introduces an acrylonitrile group or a mercaptopropenyl group, the crosslinking efficiency can be improved, so that the coating film has excellent light resistance and chemical resistance. The content of the monomer component having a carboxyl group such as acrylic acid or mercaptoacrylic acid constituting the resin is preferably in the range of 5 to 40% by weight. The weight average molecular weight of the polymer binder is preferably in the range of 1,000 to 1,000,000. By having a weight average molecular weight of 1,000 or more, the coating degree can be made uniform. Further, when 100,000 is used at 12 1309339, more excellent developability can be obtained.

Further, (b-2) a photopolymerizable monomer such as methyl acrylate, decyl decyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and ethylene Alcohol diacrylate 'ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimercapto acrylic acid S, tetraethylene glycol diacrylate vinegar, tetraethylene glycol Mercapto acrylate, propylene glycol diacrylate, propylene glycol dimercapto acrylate, trishydroxypropyl propane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetrahydroxy fluorenyl Propane tetramethacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tridecyl acrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylic acid Ester, dipentaerythritol pentadecyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, benzyl acrylate, benzyl Base acrylate, Cardo epoxy diacrylate, acrylic Methacrylic acid, etc. but is defined by this. When the component (b) is composed of the (b-Ι) component and the component (b-2), the total of the (b-Ι) component, the component (b-2), and the (c) photopolymerization initiator are 100 parts by weight. The component (b-1) is preferably formulated in an amount of 10 to 60 parts by weight. When the amount is 10 parts by weight or more, it is easy to form a film during coating and drying, and the film strength after curing can be sufficiently enhanced. Further, by setting the amount to 60 parts by weight or less, the development property can be improved. Further, among the total of 100 parts by weight of the (b-Ι) component, the component (b-2) and the (c) photopolymerization initiator, the component (b-2) is preferably formulated in an amount of from 15 to 50 parts by weight. When the amount is 15 parts by weight or more, it is possible to prevent the photocuring failure, and 13 1309339 can obtain sufficient heat resistance and chemical resistance. Further, by adjusting the amount to 50 parts by weight or less, the ability to form a coating film can be improved. The photopolymerization initiator (c) can be appropriately selected in accordance with the type of the photopolymerizable compound (b). These photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator is, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propen-1-yl, 1-(4-isopropyl-phenyl)-2-light-2-ylpropan-1-yl, 1- (4 - dodecylphenyl)-2 -transyl-2-mercaptopropan-1-ol, 2,2-dimethoxy-1,2-diphenylethane-1-one, Bis(4-didecylaminophenyl) Stuffed I, 2-mercapto-1-[4-(indolylthio)phenyl]-2-iFolinin-1-one, 2-pyryl- 2-Dimethylamino-1 - (4-norfolin phenyl)-butylene-1-pyrene, ethyl hydrazine, 1-[9-ethyl-6-(2-methylphenylhydrazino) -911-oxazol-3-yl]-,1-(0-acetamidine), 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide, 4-benzylidene- 4' - mercapto dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-didecylamino Butyl benzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoaminobenzoic acid, benzyl-/S-methoxyethyl Acetal, benzyldimethylketal, 1-phenyl-1,2- Propanedione- 2-(o-ethoxycarbonyl)anthracene, decyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethyl Sale of 嗣, 气, 1-prop-4-ethoxy n-zegitone, sale of 11 tons, 2-chloro-Serton, 2,4-diethyl thioxanthene, 2-nonyl thioxanthene, 2-iso Propyl thioxanthene, 2-ethyl hydrazine, octadecyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl hydrazine, diazobutyronitrile, benzoquinone peroxide, peroxidation Cumene, 2-Hydroxythiobenzimidazole, 2-Hetylthiol 14 1309339 曰月修修(更)正换, 换页 j τ··ί·.· !!'>

Benzobenzoxazole, 2-hydrothiobenzothiazole, 2-(o-phenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, diphenyl ketone, 2 -Chlorodiphenyl ketone, p-pair, bisdidecylaminodiphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-di-diphenyl ketone, 3,3-Dimercapto-4-oxooxydiphenyl ketone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoate Ingot butyl ether, benzoin isobutyl ether, benzoate butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-didecylamine Phenylpropiophenone, dichloroacetophenone, tri-o-acetophenone, p-butyl acetophenone, p-dimethylaminoacetophenone, p-butyl butyl trichloroacetophenone, p-butyl Acetone acetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-mercaptothioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone , pentyl-4-didecylaminobenzoate, 9-phenyl acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl) Pentane, 1,3-bis(9-acridinyl)propane, P-oxygen tri-well, 2,4,6-paraxyl (trichloromethyl)-s-tri-, 2-methyl-4,6-bis(trichloroindenyl)-s-tri. Well, 2-[2-(5-fluorenylfuran-2-yl)vinyl]-4,6-bis(trichloroindenyl)-3-tri-, 2-[2-(furan-2-yl) Vinyl]-4,6-bis(trichloromethyl)-s-tri-anthracene, 2-[2-(4-diethylamino-2-indenylphenyl)vinyl]-4, 6-double (three gas sulfhydryl)-s-three. Well, 2.-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trimethylsulfonyl)-s-tri-, 2-(4-decyloxy Phenyl)-4,6-bis(trichloroindenyl)-s-tri. Bismuth, 2-(4-ethoxystyryl)-4,6-bis(trimethylmethyl)-s-tris, 2-(4-n-butoxyphenyl)-4,6-bis ( Tri-gas methyl)-s-three. Well, 2,4-bis-trichloromethyl-6-(3-bromo-4-indolyloxy)phenyl-s-three" well, 2,4-bis-triseocarbyl-6-(2 -Bromo-4-oximeoxy)phenyl-s-tri. Well, 2,4-bis-tris-methyl- 6-(3-bromo-4-methoxy)styrylphenyl-s-tris-, 2,4-bis-trichloro 15 1309339 I The day of the month is ί F! methyl-6-(2-bromo-4-methoxy)styrylphenyl 1_3. Hey. Further, a photoinitiator-forming composition may be added to the photopolymerization initiator.

The photoinitiating aids such as diethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamine Isoamyl benzoate, 2·ethylhexyl 4-dimethylaminobenzoate, 2-didecylaminoethyl benzoate, N,N-didecyl-nonanilide, 4,4 '-Bis(monomethylamino)diphenyl ketone (commonly known as Michler; Michler, s ketone), 4,4 bis(ethylamino)diphenyl ketone, 9, ι〇_Dimethoxy Base, 2-ethyl-9,1〇-dimethoxy oxime, 9,1 fluorene-diethoxy fluorene, 2-ethyl-9,1 〇-diethoxy hydrazine, and the like. These photoinitiating aids may be used alone or in combination of two or more. In the above (d) solvent, a dialkylene glycol monoalkyl ether is used as an essential component. Further, it may contain an isomer thereof.

The above-mentioned one of the above-mentioned alkylene-alcohol-based bases, such as diethylene glycol monodecyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono N-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-n-hexyl bond, ethylene glycol monophenyl, diethylene glycol mono-2-ethylhexyl ether, two extension Propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di-n-glycolic acid monoisobutyl ether, diethylene glycol monobutyl ether, etc. . The dithiol-alcoholic monoalkyl group is represented by the following formula (1) R, 〇-CnH2n-0-CnH2n-OH (1) (wherein Ri is a linear, branched or cyclic ring having a carbon number of 1 to 8) Alkyl, 16 1309339

The solvent represented by the aryl group or the η system is an integer of 2 to 5). In particular, R1 is preferably a linear alkyl group having 1 to 8 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms or more preferably an aryl group. Moreover, η is preferably 2 or 3. Among the above solvents, in particular, dipropylene glycol monomethyl ether is preferred. Further, in order to improve the coatability and adjust the viscosity, a solvent other than the above may be blended.

The solvent is, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol didecyl ether, ethylene glycol diethyl ether , ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol didecyl ether, propylene glycol diethyl ether, diethylene glycol Dimercaptoether, diethylene glycol diethyl ether, ethylene glycol monodecyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene Alcohol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether Acid ester, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate (MBA), 4-methoxybutyl acetate, 2-methyl-3 acetate Methoxybutyl ester, 3-mercapto-3-acetate Methoxybutyl ester, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, acetic acid 2 - Methoxypentyl pentoxide, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-decyloxypentyl acetate, 3-mercapto-3-phenyl 1 171339 Amyl amyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-decyloxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, decyl isobutyl Ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, decyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, decyl 2-hydroxypropionate, 2-hydroxypropionic acid Ester, methyl 3-methoxypropionate, ethyl 3-methoxyoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-propoxypropionate, 3-methoxypropionic acid Ester, isopropyl 3-methoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,

Methyl 2-hydroxy-3-mercaptobutyrate, propyl acetate, butyl acetate, isoamyl acetate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, butyl pyruvate, methyl acetate, ethyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylhexyl lactate, benzyl methyl ether, benzyl ethyl ether, Dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, 7-butyrolactone, benzene, toluene, diphenylbenzene, cyclohexanone, butanol, 3 - Methyl-3-methoxybutanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, and the like. Among them, in particular, in terms of stability over time, it is preferred to contain 3-methoxybutyl acetate. The amount of the solvent to be used is not particularly limited, and the concentration at which the photosensitive composition can be applied to the substrate or the like is appropriately set in accordance with the required thickness of the coating film. The photosensitive composition of the present invention has a viscosity of from 1 to 100 cp, preferably from 2 to 50 cp, more preferably from 2 to 10 cp. Further, the solid content concentration is preferably 5 to 100% by weight, more preferably 10 to 40% by weight. As described above, the occurrence of foreign matter can be suppressed by using a dialkyl diol monoalkyl ether as a solvent. In particular, when carbon black is used as a coloring agent, the occurrence of foreign matter can be particularly suppressed. And more capable of suppressing formation by a photosensitive composition 18

(more) is replacing bei

1309339 &amp; The surface of the film is rough. Therefore, when the rotary coating is used, the uniformity of the film thickness can be improved. Further, the above-mentioned dialkylene glycol monoalkyl ether is preferably contained in the solvent of the photosensitive combination portion in an amount of i 5% by weight, preferably 2% by weight, preferably 5 to 15% by weight. Better. Further, in the case of the group of 3-methoxybutyl ester, 3-methoxybutyl acetate is preferably contained in the photosensitive combination solvent in an amount of 40 to 85% by weight. Further, among the above-mentioned dialkylene glycol monoalkyl ethers, a compound having a dot of 150 ° C to 210 ° C is preferred, and a compound of 17 (TC to 190) is preferred. In this range, When the coating composition of the photosensitive composition is improved, the drying property can be improved. In particular, when the coating device is applied by a slit nozzle, the problem that the photosensitive composition is dried and solidified at the slit end can be suppressed, and after coating, A drying coating film is obtained. Further, a thermopolymer, an antifoaming agent, a surfactant, etc. may be added to the photosensitive composition of the present invention. These additions may be carried out by a single or several combination of the above-mentioned thermal polymerization inhibition. The agent may be selected from well-known compounds, brewing, nitrogen, i-ethyl, etc. The above antifoaming agent may be selected from well-known compounds, such as lanthanide compounds. The above surfactants may be selected from well-known compounds, examples, cations, non- Compound such as ion system. &lt;Preparation method of photosensitive composition&gt; The total enthalpy of the coating material is 30%, the fullness of the acetic acid is selected, and the composition of the non-rotating nozzle is good. For the sole use of, for example, a hydrogen system, a fluorine such as an anion 19 97. 97. 1309339 ^ a replacement page i ------- λ. i The photosensitive composition of the present invention can be prepared by the following method (a) a coloring agent, (b) a photopolymer compound, (c) a photopolymerization agent, and (d) a solvent, and an organic additive added as necessary, and a mixer such as a 3-roll mill, a ball mill, or a sand mill (dispersion and mixing) The resin composition is filtered, for example, by a 5 micron membrane filter to prepare a photosensitive composition. <Method of Forming Light-Shielding Layer (Black Matrix)> Hereinafter, an example of a method of forming a black matrix will be described as a photosensitive composition for forming the invention In one embodiment of the light-shielding layer method, a photosensitive composition composed of an opacifier as a coloring agent is first applied by a roll coater, a reverse roll coater, a bar coater, or the like, a contact transfer type coating or a spinner (rotary coating). A non-contact type coating device such as a device, a curtain coater, or a non-rotating applicator such as a fine cloth is coated on the substrate. The substrate ' can be made of a light-transmitting substrate, for example, a glass plate 0. The photosensitive composition is After coating After drying to remove the solvent, the negative mask is placed in the middle, and the active energy light such as ultraviolet rays and quasi-split light is exposed to expose a part of the area. The exposure can be directed to a mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp. The light source emitting purple light, the energy line of the irradiation varies depending on the composition of the photosensitive composition, preferably about 30 to 2000 mJ/cm 2 . The developed film is developed by a developing solution to form a black moment developing method. It is particularly limited, for example, a dipping method can be used, and a mist is not used. A pre-wet method can also be used. In order to improve the purpose of curing the photoresist film of the developer after image formation, post-baking, post-curing, etc. may also be employed. By, and then use the 〇 ' to make the cloth sewed into the glass base 0 lei use an outer line such as array. .Wait. Drying and developing 20 1309339 A specific example of the liquid, for example, an organic compound such as monoethanolamine, diethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt. &lt;Method of forming color filter&gt;

The photosensitive composition is applied to the substrate on which the black matrix is formed in the same manner as described above, and the colored layer of a predetermined color is patterned (stripes or dots) at predetermined positions (openings) of the black matrix through drying, exposure, and development. Wait). For example, when RGB color filters of red (R), green (G), and blue (B) are produced, the photosensitive composition containing colorants of R, G, and B colors is used, and the above process is repeated to form 3-color coloring layer. As described above, a color filter can be formed. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. (Resin Synthesis Example 1) First, the compound 1 represented by the following formula (I) was synthesized according to the method described in JP-A No. 2001-35473. That is, in a 500 ml four-necked flask, 235 g of bisphenol quinone type epoxy resin (epoxy equivalent 23 5), 110 mg of tetramethylammonium chloride, and 100 mg of 2,6-di- 3rd were sequentially added. The base-4-cresol and 72.0 g of acrylic acid were blown into the air at a rate of 25 ml/min, and dissolved by heating at 90 to 100 °C. Next, the solution was gradually heated while the solution was cloudy, and heated to 120 ° C to be completely dissolved. Here, the solution gradually became a transparent viscous and continued to stir. During this period, the acid value was measured until it was less than 1.0 mg KOH/g, and 21 1309339 was heated and stirred. It takes 12 hours for the acid price to reach the target. Subsequently, the mixture was cooled to room temperature to obtain a colorless transparent, solid bisphenolphthalein type oxyacrylic acid represented by the formula (III). [Chemical Formula 3]

Next, 600 g of propylene glycol monodecyl ether acetate (PGMEA) was added to 307.0 g of the above bisphenol-type epoxy acrylate obtained by the method, and after dissolution, 8 0.5 g of diphenyl ketone tetracarboxylic acid was mixed. The anhydride and 1 g of tetraethylammonium bromide were slowly warmed up and reacted at 11 〇 to 11 5 ° C for 4 hours. After confirming the disappearance 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 the compound 1 represented by the above formula (I). The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

Here, the compound 1 is a compound of the formula (I) wherein X is a group represented by the formula (II), and Y is an acid anhydride group removed from 1,2,3,6-tetrahydrofurfuric acid dianhydride (-0: Residue after 0-0-(:0-), 7 is the residue after removal of the anhydride from 3,3',4,4'-diphenyl ketone tetracarboxylic acid tetrahydride, and Y/Z molar ratio 50.0/50.0. This compound was used as a main photopolymerizable compound to prepare a photosensitive composition of the present invention. (Examples 1 to 5 and Comparative Examples 1 to 4) Use: 22 1309339 __ "_ . More) is replacing 1 ,·~·^&lt; -.^r-·'^^·.··' τ- 地 '' &quot;&quot; (a) Ingredients, (a-1) carbon dispersion CF black EX- 1 45 5 (high-resistance carbon: 24%, dispersant 5%, non-volatile component: 29%, solvent: 3-methoxybutyl acetate, manufactured by Royal Pharmaceutical Co., Ltd.) 100 parts by weight. (b) Ingredient, (b-1) Compound 1 above (55% solid content, solvent: 3-methoxybutyl acetate (MBA), molecular weight 3400) 40 parts by weight (b-2) dipentaerythritol tetraacrylate 10 parts by weight

(c) Ingredient, (c-1) ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-indazol-3-yl]-, l-(0-B醯肟), (CGI 242): manufactured by CIBA SPECIALTY CHEMICALS) 2 parts by weight of (c-2) 2-benzyl-2-didecylamino-1-(4-morpholin phenyl)-butane- 1 ketone, (IRUGACURE 3 69: manufactured by CIBA GEIGY Co., Ltd.) 1 part by weight. Moreover, component (d) is used: (d-Ι) dipropylene glycol monomethyl ether (DPM) (d-2) 3-methoxybutyl acetate (MA) (d-3) cyclohexanone (d-4) Propylene glycol monomethyl ether acetate was adjusted so that the solid content concentration was 16% by weight, and the amount of the solvent was adjusted in accordance with the ratio of the total solvent of the photosensitive composition shown in Table 1. [Table 1] Solvent (1 1: Amount %) Foreign matter number (d-1) (d-2) (d-3) (d-4) 23

I30933f Example 1 30 60 10 Example 2 20 80 λ Meaning -- Example 3 20 1 70 V- -; - Example 4 10 80 ---- 10 3 —^........ Example 5 10 __ 90 • 〇^----. 0 Comparative Example 1 - 100 _ ^ 1 Comparative Example 2 - 90 10 1 Comparative Example 3 80 20 1 j '--- Comparative Example 4 - 60 20 20 9

The present micron membrane filter composed of the above components was filtered, and the compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were mixed by a stirrer for 2 hours to pass through 5 photosensitive compositions. Non-rotating applicator using a slit nozzle (TR454 1 〇: manufactured by Tokyo Ohka Co., Ltd.), on a glass substrate with a clean surface (68 mm "Μ mm X 0.7 mm") The photosensitive composition obtained in the above manner was coated with a thickness of 14 μm. The film was dried for 2 minutes to form a film (photosensitive layer) of the photosensitive composition. Then, by visual observation and metal display The micro φ mirror was used to calculate the number of foreign matter on the photosensitive layer on the glass substrate using a Na lamp. The results are shown in Table 1. The agglomerates of the components of the foreign matter (4) were considered. As described above, the number of foreign matter in the examples was 5 or less. Practically, it is a generally acceptable grade 'but the number of foreign objects in the comparative example exceeds 5, which is a practically problematic grade. (Evaluation of surface roughness) Moreover, since the coating is sincerely extended from 7 to Example 3, The photosensitive 24 1309339 composition of Comparative Examples 2 and 4 was measured for surface roughness (Ra) of the film after drying using an atomic force microscope (AFM), and the results are shown in Table 2. [Table 2] Surface roughness Ra (A) Example 3 13.2 Comparison 2 15.9 15.1 Comparative Example 4

As in the above, Example 3 using a dialkylene glycol monoalkyl ether had a good surface roughness. (Evaluation of film thickness uniformity) Further, the photosensitive compositions of Example 5 and Comparative Example 1 were coated on a 550 mm X 650 mm glass substrate using a rotary coater, and the thickness of the film was measured from the edge of the substrate. As a result, as shown in Fig. 1, it can be clearly seen from Fig. 1 that the uniformity of the film thickness can be improved by using a dialkyl diol monoalkyl ether. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the uniformity of film thickness of the photosensitive compositions of Example 5 and Comparative Example 1. [Main component symbol description] None 25 8

Claims (1)

1309339 :» '一''r一一一一一一一一-]-'一一, -_____一:, -二一- j Ί ;:二;· .. ' ' :''':^ .. .— : X. Patent application scope: _ 1. A photosensitive composition containing (a) a colorant, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and (d) a solvent, and by using A photosensitive composition coated by a coating method of a fine nozzle containing a diethylene glycol monoalkyl ether as (d) a solvent. 2. The photosensitive composition according to claim 1, wherein the alkyl glycol monoalkyl ether is represented by the following formula (1): R1-0-CnH2n~〇-CnH2n-OH (1) (wherein R1 A solvent represented by a straight chain, a branched chain or a cyclic burning or aryl group having 1 to 8 carbon atoms, and an integer of 2 to 5 in the η system. 3. The photosensitive composition of claim 2, wherein the photosensitive alkyl group is a linear alkyl group having 1 to 4 carbon atoms. 4. The photosensitive composition according to claim 2 or 3, wherein η is 2 or 3. 5. The photosensitive composition of claim 2, wherein the solvent is diethylene glycol monomethyl ether. 6. The photosensitive composition of claim 2, wherein the content of the solvent is the weight % of the total solvent of the photosensitive composition. 7. The photosensitive composition of claim 1, wherein more (3-)oxybutyl acetate is used as the (d) solvent. 8. The photosensitive composition of claim 7, wherein the conjugated singular base is extended, and the formula (1) (1) 1 to 50 contains acetic acid 26 1309339 The content of the 3 - methoxy butyl ester is 50 - 85% by weight in the total solvent of the photosensitive composition. The photosensitive composition of the first aspect of the invention, wherein the (a) coloring agent is Carbon black. 27 1309339 VII. Designated representative map: (1) The designated representative figure of this case is: Figure 1 (2), the representative symbol of the representative figure is a simple description: none 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: