TW200819913A - 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 polybasic acid anhydride (a-3) comprises a polybasic acid anhydride having at least two benzene rings.

Description

200819913 IX. OBJECTS OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, and more particularly to a colored photosensitive resin composition 'for forming a black color used for a color filter A light-shielding film at a matrix or the like. [Prior Art]

Conventionally, as a method of producing a color filter using a pigment, a dyeing method, an electrodeposition method, an inkjet method, a pigment dispersion method, and the like are known. In the case of the pigment dispersion method, a photosensitive resin which is sensitized by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, or the like to a coloring composition (dispersion of a pigment using a dispersing agent or the like) The composition was applied onto a glass substrate, dried, and exposed and developed to form a colored pattern. Subsequently, heating is applied to fix the pattern to form a pixel. These steps are repeated for each color to form a color filter. ^ / Ba Ying's color-sensitive photosensitive resin used in the film of the film = sufficient resolution for the object, adhesion of the ruthenium substrate, low development image retention +: property. In addition, when it is formed by the pigment dispersion method, it is possible to supply light, and it is required that no part of the removal step can be produced or contaminated, and the removal part can improve the η barrier, and the knives must be sufficiently dissolved. Pattern formation such as sex and sharpness of the edge of the pattern. In particular, if the black matrix is required in the light capability, the right axis is not imaginary, the main wavelength Q domain has a difference in the ..., and the cross-linking difference between the exposed portion and the unexposed portion is very difficult; The exposure portion is sufficiently cured, but it is sufficiently hardened on the side of the irradiation surface of the light 5 200819913, but there is a problem that the side surface of the substrate is not hardened. Further, since a large amount of black colorant which is insoluble in the developing liquid is mixed 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 used as a binder resin by using a reaction product of a carboxyl group-containing acrylate resin and an alicyclic epoxy group-containing compound. Further, the present invention discloses a color-sensitive photosensitive resin composition (see Patent Document 3), which contains a polycarboxylic acid resin which is a reaction product of an oxygen compound having two epoxy groups and a monocarboxylic acid. It is obtained by reacting with an acid anhydride. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. 2004-43 No. [Problems to be Solved by the Invention] However, even in the resin composition described in the above Patent Documents 1 to 3, there are problems such as insufficient sensitivity, poor adhesion to pixels, easy peeling, and residual residue. . In addition, since the development margin is small, the problem of the exposure time of the photo will be peeled off and the edge of the pixel will be shaken. In view of the above problems, the present invention provides a coloring photosensitive resin composition 6

In the case of the above-mentioned problem, the inventors of the present invention have repeatedly developed a black matrix image which is excellent in linearity and does not have a residue and which is excellent in contrast. The optical composition containing a functional group excellent in photoreceptivity can solve the above problems, and the present invention is completed. The present invention provides the following. The present invention provides a colored photosensitive resin composition polymerizable compound (A), a photopolymerization initiator (B), and a colored enamel photosensitive resin composition, and the photopolymerizable compound (Α)-based compound (a-1) a resin obtained by reacting a reaction product containing an unsaturated carboxylic acid (a-2) with an acid anhydride (a-3), and a compound of at least two benzene rings of the above polybasic acid anhydride. [Efficacy] According to the colored photosensitive resin composition of the present invention, a polybasic acid anhydride having at least two benzene rings is used as the material of the photopolymerizable compound in the photosensitive resin composition. A colored photosensitive resin composition which is excellent in balance between sensitivity and solubility and excellent in adhesion of a substrate at the edge of a pixel. It is easy to use a color filter with a high contrast and a beautiful color of R, G, and B. There will be a peeling off. As a result, fat was applied to the invention. In addition, the color containing the light IJ (C) contains the epoxy and the poly (a-3), and can be used as the resin to be colored, and can be sharpened and provided. 7 200819913 [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described. The colored photosensitive resin composition (hereinafter also referred to as "composition") of the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), and a color former (C). [Photopolymerizable Compound (A)]

The photopolymerizable compound (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. The respective components are described below. <Epoxy compound (al)&gt; The epoxy compound (hereinafter also referred to as component (a-1)) used in the present invention is not particularly limited, and examples thereof include For example, epoxy propyl ether type, epoxy propyl ester type, epoxy propyl amine type, alicyclic type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, naphthalene type, anthraquinone type A phenol novolac type or an o-cresol type epoxy resin. Among them, a biphenyl type epoxy resin is preferred. The biphenyl type epoxy resin has at least one or more of the following formula (5) in the main chain. The biphenyl skeleton has at least one epoxy group. Further, the component (a-1) is preferably one having two or more epoxy groups.

(In the formula, a plurality of R3 groups each independently represent a hydrogen atom, a carbon number of 1 to 12, 8 200819913 alkyl group, an i atom or a phenyl group which may have a substituent, and 1 represents an integer of 1 to 4; Further, in the biphenyl type epoxy resin, an epoxy resin represented by the following formula (3) is preferably used, and an epoxy resin represented by the following formula (4) is particularly preferable. By using the compound of the formula (4), it is possible to provide a composition excellent in balance of sensitivity and solubility. Further, the component (a-1) may be used singly or in combination of two or more. [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) [Chemical Formula 3 ]

Further, in the formulas (3) and (4), m is an average value and represents the number of 0 to 10. The m is preferably less than 1. &lt;Unsaturated Carboxylic Acid (a-2)&gt; The unsaturated carboxylic acid (hereinafter also referred to as "(a_2) 200819913 component") used in the present invention to contain a propylene group in the molecule Group) and a monocarboxylic acid having a reactive unsaturated double bond such as a methacrylic group is preferred. Examples of such an unsaturated group-containing carboxylic acid include acrylic acid, mercapto acrylic acid, styryl acrylic acid, /3-mercaptoacrylic acid, α-cyano cinnamic acid, cinnamic acid and the like. 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, dodecyltrimethylammonium chloride or chlorine may be mentioned. 4th ammonium salt such as tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, acridine, triphenylphosphine, etc. as a catalyst, reacted in an organic solvent at a reaction temperature of 50 to 150 ° C ~ dozens of hours of method. The amount of (a-1) component and (a-2) component used in the reaction is such that 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 component (a-1) to the component (a-2) is from 1:0.5 to 1:2, the crosslinking efficiency tends to be improved, which is preferable. &lt;Polyhydric acid anhydride (a-3)&gt; The polybasic acid anhydride (hereinafter also referred to as "(a-3 component)") used in the present invention is a polybasic acid anhydride having two or more carboxyl groups, and has at least two a compound of a benzene ring. The (a-3) component may, for example, be an acid anhydride having a biphenyl skeleton represented by the following formula (1) and an acid anhydride in which two benzene rings represented by (2) are bonded by an organic group. 10 (1)200819913 [Chemical Formula 4]

(In the formula, by photopolymerization, and the composition is further, butene hexahydrophthalic anhydride, and R2 means an alkylene group which may have a substituent having a carbon number of 1 to 10). An anhydride having a carboxylic acid having two or more carboxyl groups, and at least two benzene rings can be introduced into the conjugated compound. By using such a compound, it is possible to provide a color-sensitive photosensitive resin having excellent sharpness and solubility in the balance of sensitivity and solubility, and the (a-3) component has at least two benzene rings in addition to the above. The acid anhydride may contain other polybasic acid anhydrides. Examples of the other polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, acid anhydride, mercapto hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, benzene trimellitic acid anhydride, and diphenyl. Ketone tetracarboxylic dianhydride, 3-methylhexahydro&amp; π 200819913 anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydroanthracene An acid anhydride, 3-methyltetrahydro-glycolic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetraphthalic anhydride, 4-ethyltetrahydrophthalic anhydride, etc., which may be used singly or in combination 2 More than one species.

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 of the component (a-1) and the component (a-2) and the acid anhydride group of the component (a-3) are 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 mg/g is preferred, and more preferably 70 g KOH/g or more and 110 g KOH/g or less. When the acid value of the resin is 10 mgKOH/g or more, sufficient solubility can be obtained in the developing solution, and sufficient acidity can be obtained by setting the acid value to 150 mgKOH/g or less. It is possible to make the surface properties good. Further, the weight average molecular weight of the resin is preferably from 1,000 to 4,000, and more preferably from 2,000 to 3,000. By setting the weight average molecular weight to 1,000 or more, heat resistance and film strength can be improved. Further, by 40,000 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 ethylenic 12 200819913 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.

The monofunctional monomer may, for example, be (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxy decyl (meth) acrylamide ethoxymethyl (methyl) Propylene decylamine, propoxymethyl (meth) acrylamide, butoxymethoxy methoxy (meth) acrylamide, acrylic acid 'maleic acid, maleic anhydride, itaconic acid, Ikonic anhydride, citraconic acid, citric acid anhydride, crotonic acid, 2 propylene acrylamide 2-methylpropane sulfonic acid, t-butyl acrylamide decyl sulfonate, decyl (meth) acrylate, (fluorenyl) 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-(indenyl) propylene oxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate , (meth) isopropyl tetrahydrofurfuryl ester, dimethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate (A ) 2,2,3,3-tetrafluoro-propyl acrylate, phthalic acid derivative half (Yue-yl) acrylate, N- methylol (Yue-yl) acrylamide and the like. Further, these may be used alone or in combination of two or more. On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(decyl)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(decyl) group. Acrylate, polypropylene glycol di(meth)acrylic acid 13

200819913 Ester, butanediol di(mercapto) acrylate, neopentyl glycol bis(indenyl) ester, 1,6-hexanediol di(methyl)propanoate, trimethylolpropane triacrylate , glycerol di(decyl) acrylate, neopentyl alcohol tripropylene neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, diol hexaacrylate, dipentaerythritol di(meth)acrylic acid Ester, neotris(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, tetraol penta(meth)acrylate, dipentaerythritol hexa(methyl)propene 2,2-dual ( 4-(Methyl)propenyloxydiethoxyphenyl)propane, (4-(indenyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3. Acryloxypropane Base (mercapto) acrylate, ethylene glycol dimethacrylate (meth) acrylate, diethylene glycol dicyclopropyl ether bis(indenyl) acrylic acid diepoxypropyl bis (meth) acrylate Ester, glycerol tripropylene glycerol polyepoxypropyl ether poly(indenyl) acrylate, (meth) acrylate (ie, phthalmethylene diisocyanate), tridecyl hexamethylene fluorene Reaction of acid ester and hexamethylene diisocyanate with 2-hydroxyl (meth)acrylic acid, fluorenyl bis(indenyl) acrylamide, (fluorenyl) propylene decyl ether, polyol and N-hydroxyl A condensed functional monomer of methyl (meth) acrylamide or tripropylene acetal. Further, these may be used alone or in combination of two or more. The content of the monomer of the ethylenically unsaturated group is preferably 5% by mass or more and 50% by mass, and more preferably 10% by mass or more and 40% by mass or less based on the solid content of the coloring photosensitive resin composition. The range of reliance, the balance of sensitivity, imaging, and resolution, and the tendency to have a tendency are better. Acrylic (meth) acid S, neopentyl pentaerythritol dipivalate, 2,2·bis-(methyl) ether diester, acid ester, acid amine diisocyanoethyl ester Amines and the like are used in a large amount, and are also available in an amount of up to 14 200819913 [Photopolymerization Initiator (B)] Further, a photopolymerization initiator (hereinafter also referred to as "(B) component"),

Acetylene, 2,2-diethoxyethyl benzene, p-dimethyl acetophenone 'p-dimethylamino propyl benzene, dichloro ethane benzene, trichloro ethane benzene, third butyl Ethylene benzene such as acetophenone or diphenyl ketone such as diphenyl ketone, 2-chlorodiphenyl ketone, p-p-didimethylaminodiphenyl ketone, or benzyl or benzene Amarantry, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, or benzyl dimethyl ketal, thioxanthene, 2-chlorothioxene, a sulfur compound such as 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, or 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene An anthraquinone such as 2,3-diphenyl, or an organic peroxygen such as azobisisobutyronitrile, benzamidine peroxide or cumene peroxide, or 2-hydrothiobenzimidazole, a thiol compound such as 2-hydrothio benzoxazole or 2-hydrothiobenzothiazole, or 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl An imidazolyl compound such as a dimer or a tri-till compound such as p-methoxytriazine or 2,4,6-para(trichloromethyl)-s-tritium or dimethyl _4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloroindenyl)-s - Three-plowing, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl three-pile, 2-[2-(4·diethylamino-2-indenyl) Phenyl)vinyl]-4,6-bis(trichloromethyl)-s-triterpene, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-double (Trichloroindolyl)-^trimium, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triterpene, 2-(4-ethoxystyrene Base)· 4,6-bis(trichloromethyl)-s-tripper, 2-(4-n-butoxyphenyl)-4,6-bis(triseodecyl)-s-triterpene, etc. a tritrap compound having a halofluorenyl group, or a 2-benzyl group 15 200819913 -2-monomethylamino-1-(4. saccharin (m〇rph〇lin〇)phenyl)-butane] ketone The above-mentioned photopolymerization initiator may be used singly or in combination of two or more kinds thereof. The total amount of the solid component other than the solvent is 100 parts by mass, and the content of the photopolymerization initiator is 1 part by mass to 150 parts by mass. The portion is preferably 5 parts by mass to 100 parts by mass, more preferably 1 part by mass to 50 parts by mass. When the content is 15 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 photohardening failure can be suppressed. )]

The colored photosensitive resin composition of the present invention contains a coloring agent (hereinafter also referred to as "(C) component"). Colorants can be moved, for example, as a pigment in a colorimetric index (CI; issued by The Society of Dyers and Colourists). Specifically, the following colorimetric index (CI) is used. ) No. Net! CI·Pigment Yellow 1 (under ·, "C.I. Pigment Yellow" is the same, only the number is recorded), 3, 11, 12, 13, and > 14, 15, 5, 16, 17, 20, 24, 3 1 ' 53 ' 55 &gt; 60' 61% 65' 71 , 73 , 74 , 8 1 , 83 ^ 86 - 93 , 95 , 97 , 98 ^ 99 ^ 100 - 101 &gt; 104 - 106, 108 , 109 '11 0 , 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148 '150, 151, 152, 153, 154, 155 ^ 156, 166, 167 , 168, 175, 180, 185; 16 200819913

C. I · Yan and Pan Orange 1 (hereinafter, "C, ► I. Pigment Dial" is the same as the number only), 5 &gt; 13 , 14 , 16 , 1 7 , 24 , 34 , * 36 ' 38 , 40 ^ 43 , 46 , 49 , 5 1 '55 , 59 , 61 , 63 , 丨 64 , 71 , 73 ; CI Pigment Violet 1 (hereinafter, "C' .I. Pigment Violet" is the same as the number only) ' 1 9 ' 23 &gt; 29 ' 30 ^ 32, 36, 37, 38, 39, 40, 50 ; C· I. Pigment Red 1 (hereinafter, "C, .I. Pigment Red" is the same as the record number), 2 ' 3 ^ 4 , 5, 6, 7 ' 8 x 9, 1 0 '11 , 12, 1, 4^15 , 1 6 , 17 \ 18 , 19 , 21 , 22 , 23 , 30 , 3 1, , 32 , 37 , 3 8, 40, 41, 42 &gt; 48 : Bu 4 8 : 2 &gt; 4 8: 3, 48 ·· 4, 4 9 ··1, 49 : 2, 50 ·· 1, 52 : Bu 53 : Bu 57 ' 57 : 1, 57 : 2, 58 · 2, 58 : 4, 6 0 : 1, 63 : 1, 63 : 2, 64:1, 81 : 1 &gt; 83, 88 ^ 90 : 1 , 97 , 101, 102 ' 1 04 ' 105 , 106 , 108 , 112 , 113 , 114 122 , 123 , '144 , 1 46 , 149 , 15 0 , 15 155 &gt; 1 66 , 168 170 ^ 171, 172 &gt; 1 74, 175, 17 6 , 177, 178, 179, 180, 185, 187, 188 ' 1 90 ' 192 , 193 , 194 , 202 ^ 206 , 207 208 , 209 , 215 , 216 , 217 &gt; 2 20, 223 ^ 224, 226 ' 227 , 228 ^ 240 &gt; 242 , 243 , 245 , 254 , 25 5 , 264 , 265 j CI Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" The same 5 only record number) '2 '15 ^ 15 ·· 3 ' 15 : 4, 15:6 , 16, 22, 60, 64 ^ 66 ; C · I. Pigment Green -7, CI . Pigment Green - 3 6 , C · I. Pigment Green-3 7 ; C · I · Yan; Branch Brown 23, CI Yan $ 14 Brown 25, CI Pigment Brown 26, C.I_ Yan·f Brown 28; C. I · Yan i 钭 Black 1. C.I_ _Pigment Black 7. Further, when a black matrix is formed, the component (C) is preferably a black pigment. 17

200819913 Also, black pigments are preferably carbon black. Further, metal oxides such as titanium black, copper, iron, knot, chromium, nickel, zinc, #5, silver, composite oxides, metal sulfides, metal sulfates or metal carbonates may also be mentioned. Among these black pigments, carbon black having a high light-shielding property is more preferable. By using the above-mentioned photopolymerizable compound, a coloring photosensitive resin having high adhesion and excellent image retention can be obtained by using a black pigment having a high light-shielding property. 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. It is also possible to coat the carbon black with a resin. 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 produce a low power consumption with less leakage and high reliability. Device. Further, the above organic pigment may be appropriately added as an auxiliary pigment to adjust the color tone of the carbon black. Further, a dispersant for uniformly dispersing a colorant is preferably a polyethylene-based, urethane-based or acrylic-based polymer powder, particularly when carbon black is used as a 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, 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 used in an amount of from 10 parts by mass to 80 parts by mass. The volume is preferably in the range of 20 parts by mass to 40 parts by mass. The above-mentioned inorganic pigments and coloring are also known to be used for the purpose of stretching and dispensing. 18 200819913 The organic pigment is preferably dispersed in a photosensitive resin composition after being dispersed in 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, based on the solid content of the coloring photosensitive resin composition. The mass% 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 OD value of 1 μm per film thickness is 4 or more, and a black matrix as a liquid crystal display is used, sufficient display contrast can be obtained. [Other components] The coloring photosensitive resin composition of the present invention can be formulated with an additive as necessary. Specific examples thereof include a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent. 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 monodecyl ether, 19 200819913

Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, di- propylene glycol monomethyl ether, di-n-ethylene glycol monoethyl ether, di-n-glycol-n-propyl ether, two (poly)alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tri-n-propyl propylene glycol monomethyl ether, tri-n-propyl propylene glycol monoethyl ether; Ethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol (poly)alkylene glycol monoalkyl ether acetates such as ethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran And other ethers; ketones such as methyl ethyl ketone, cyclohexane, 2-heptanone, and 3-heptanone; lactated alkyl groups such as 2-hydroxylpropionate and ethyl 2-hydroxypropionate Ester; 2·hydroxy-2-methylpropionic acid ethyl ester Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycol Ester, decyl 2-hydroxy-3-mercaptobutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy butyl propionate, ethyl acetate , n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl decanoate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyl Isopropyl acrylate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate, 2-ethyloxybutyrate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; decylamines such as N-methylpyrrolidone, N,N-dimethyldecylamine, and N,N-dimercaptoacetamide class. These solvents may be used alone or in combination of two or more. 20

200819913 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 methyl ethyl Ether, cyclohexanone, and 3-butylbutyl acetate show excellent solubility in photopolymerizable compounds and photopolymerization initiation, and at the same time, the properties of insoluble components such as pigments can be improved. Preferably, propylene glycol monodecyl ether acetate 3-methoxybutyl acetate is particularly preferred. The solvent may be used in an amount of from 1 part by mass to 500 parts by mass per 100 parts by mass of the total amount of the photopolymerizable compound polymerization initiator and the coloring agent. Further, as the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether or the like can be used. An antimony-based or fluorine-based compound can be used as the antifoaming agent; and the surfactant can be formed by using 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, as described later. 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 polymer may be further contained as a binder. The binder can be appropriately selected in accordance with the purpose of improving compatibility such as compatibility, film formability, and adhesion. The thickness of the black matrix formed on the substrate can be generally set in the range of 1 to 10 μm, preferably 1.5 μm to 8 μm, and 2 μm. The meter is better. When the thickness is 1.5 μm or more, not only a black matrix for a usual color filter but also a black matrix which is a color filter for spraying can be used. The colored photosensitive resin composition of the present invention can be obtained by using a kiln, a methoxyphore, an ester, a light, and an ionic agent. Pattern grease group, and adhesion imaging micron micro as an ink mixer 21 200819913 Mix the above ingredients and wide m # S*J f . Alternatively, a filter can be used to filter the mixture to be a uniform. [Method of Forming Shirt Color Polishing Sheet] 'Please describe the method of coloring the photosensitive resin composition by using the colored light-emitting sheet of the present invention. &lt;Formation of black matrix (formation of "coloring layer"), first, "coloring agent of the present invention", using a roller, and a color photosensitive resin composition (including black printing) Type coating @b coating benefits, reverse roll coater and bar coater, etc. Contactless etc.: Rotator. (Rotary coating device, the basis of transparency of the coating applicator is coated on the substrate. The substrate can be used It has optical properties: β. The adhesion of the glass substrate to the color-sensitive photosensitive tree composition can also be coated with a decane coupling agent in advance on the glass substrate. Alternatively, the coloring photosensitive resin can also be prepared. For example, a decane coupling agent is added to the product. The coloring photosensitive wire 4, the tree, and the auxiliaries are applied and dried to remove the solvent. The drying method is not particularly limited, and for example, any of the following methods can be used. '(1) On the hot plate below, preferably 9 (rc above I 0 0 〇C temperature, check a η 4 / 丨, E 1 η Λ dry for 60 seconds to l2 〇 seconds, ( 2) Place the method at room temperature for several hours to several days '(7) in a warm air heater or A method of removing the solvent by placing the anode heater for a few tenths to several hours. Next, the negative mask is placed in the middle to irradiate the active energy rays such as ultraviolet rays and excimer laser light to perform partial exposure. The amount of the wire varies depending on the composition of the photosensitive resin composition, and is preferably, for example, about -2 22 200819913 to 2000 mJ/cm 2 . Next, the exposed film is developed by a developing liquid to be patterned into a desired shape. The development method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing liquid include organic substances such as monoethanolamine, diethanolamine, and triethanolamine, or sodium hydroxide, potassium hydride, and carbonic acid. An aqueous solution of sodium, ammonia, and a quaternary ammonium salt, etc. Next, the developed pattern is post-baked at about 200 ° C to form a black matrix. Further, it is preferred to expose the formed pattern to the entire surface.

The formed black matrix can also be used as a spacer or an inkjet partition depending on the shape and thickness of the pattern. (1) Forming a color filter by lithography on a substrate on which a black matrix is formed, using a colored photosensitive wax composition containing a coloring agent of three primary colors of R, G, and B, and forming the black matrix Likewise, each color forms a colored layer in sequence. Thereby, color filters and light sheets can be formed. (2) When a color filter is formed by an inkjet method, a color filter is formed by an inkjet method, and an inkjet color filter formed of the colored photosensitive resin composition of the present invention is used. Partition wall (hereinafter referred to as the partition wall). Because the partition is black, it can also be used as a task for the black matrix. Specifically, first, the inks of R, G, and B are ejected by inkjet to a portion surrounded by the partition wall, and are accumulated in the partition wall. Next, the accumulated ink is hardened using heat or light. Thereby, a color filter can be formed. 23 200819913 [Examples] [Example 1]

400 grams of epoxy compound EPICOAT YX 4000H (manufactured by JAPAN EPOXY RESIN, epoxy equivalent 190), 5 g of triphenylphosphine, 153 g of acrylic acid, and 600 g of 3·decyloxybutyl acetate, and Let it react at 90~100 °C. Subsequently, Resin A was obtained by adding 360 g of biphenyltetracarboxylic anhydride and 40 g of tetra-glycolic anhydride (THPA) as a polybasic acid anhydride and further reacting it. The resin A had a mass average molecular weight of 7,000 as measured by GP C and an acid value of 90 mg KOH/g. Mix 150 g of the above resin A, 30 g of dipentaerythritol hexaacrylate, 12 g of 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3- Base; l· Ethyl ketone-1-(0-acetamidine) (trade name: IRGACURE OXE 02, manufactured by CIBA SPECIALTY CHEMICALS), 6 g of thiothiobenzimidazole, 4 g of 2,4·bis (three gases) Methyl)-6-(3-bromo-4-methoxy)phenyl-s-triterpene, 7 g of pigment liquid (trade name: CF black, carbon black 24%, manufactured by Royal Gum Co., Ltd. 5 g of 3-methoxybutyl acetate was used to prepare a colored photosensitive resin composition. [Example 2] Resin B was synthesized in the same manner as in Example 1 except that only 480 g of the compound (7) of the following formula was used as the polybasic acid liver. The resin I had a molecular weight of 7800 Å and an acid value of 85 KOH KOH/g. This resin B was used to modulate the colored photosensitive resin composition. [Chemical Formula 5] 24 200819913

[Example 3]

Resin C was synthesized in the same manner as in Example 1 except that 450 g of the compound of the formula (7) and 40 g of tetrahydrophthalic anhydride were used as the polybasic acid anhydride. The resin C had a molecular weight of 6,700 and an acid value of 90 g KOH/g. This resin C was used to prepare a colored photosensitive resin composition. [Example 4] Resin D was synthesized in the same manner as in Example 1 except that only 420 g of biphenyltetracarboxylic acid was used as the polybasic acid anhydride. The resin D had a molecular weight of 6,500 and an acid value of 100 mg KOH/g. This resin D was used to prepare a colored photosensitive resin composition. [Example 5] In Example 4, the reaction time was extended to synthesize the resin E. The resin E had a molecular weight of 29,000 and an acid value of 100 g KOH/g. This resin E was used to prepare a colored photosensitive resin composition. [Comparative Example 1] Resin 25 200819913 F was synthesized in the same manner as in Example 1 except that 250 g of the compound represented by the following formula (6) and 100 g of tetrahydrofurfuric anhydride were used as the polybasic acid anhydride. The resin F had a molecular weight of 430,000. This resin F was used to prepare a colored photosensitive resin composition. [Chemical Formula 6]

[Comparative Example 2] Resin G was synthesized in the same manner as in Example 1 except that only 2,200 g of tetrahydrophthalic anhydride was used as the polybasic acid anhydride. The resin G has a molecular weight of 3 8 00. This resin G was used to prepare a colored photosensitive resin composition. [Comparative Example 3] Resin oxime was synthesized in the same manner as in Example 1 except that only 40 g of the compound of the formula (6) was used as the polybasic acid anhydride. The resin oxime has a molecular weight of 5 00. This resin ruthenium was used to prepare a colored photosensitive resin composition. (Formation of a black matrix) The colored photosensitive resin compositions of the examples and the comparative examples were applied onto a glass substrate, and baked at 90 ° C for 120 seconds to form a film (prebaked film) having a thickness of 1.5 μm. Subsequently, the formed film was exposed through a reticle, and developed using an alkali developing solution (trade name: N-A3K, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to form a pattern. 26 200819913 Subsequently, the formed pattern was post-baked for 30 minutes at 2 2 〇 °c using a circulating oven to form a black matrix with a line width of 1 μm. (Evaluation) With respect to the colored photosensitive resin composition prepared in the above Examples and Comparative Examples and the black matrix formed, the development margin, the pattern straightness, the sensitivity, and the developing time of the developing solution were confirmed. The results are shown in Table 1.

Further, the evaluation method is as follows. Sensitivity: The amount of exposure is varied to minimize the amount of exposure necessary to form a pattern. Pattern linear advancement (linear advancement): visually determine whether the edge of the formed 10 micron line is shaken, 〇 when not shaken, and X when shaken. Development margin: When developing at a exposure amount of 1 〇〇mJ/cm2, the time during which the pattern can be formed without leaving the pattern unpeeled, the straightness of the pattern is good, and the residue is not formed is measured. Development solution dissolution time: A time period in which the film was pre-baked to the time of complete dissolution when a developing solution of N-A3K : 3 = 1 : 19 (weight ratio) was spray-coated at 25 ° C. [Table 1] Sensitivity (m J/cm 2 ) Pattern Linear Advancing Development margin (sec) Developing solution dissolution time (sec) Example 1 60 〇 18 31 Example 2 65 〇 20 36 Example 3 6 5 〇 19 32 Example 4 65 〇 23 38 Example 5 65 〇 25 40 27 200819913 Comparative Example 1 90 X 5 15 Comparative Example 2 95 X 7 12 Comparative Example 3 90 X 8 11 According to Table 1, two anhydrides were used. A compound of a benzene ring is synthesized to obtain a resin, and a colored photosensitive resin composition which is a photopolymerizable compound is used as the resin, and a light-shielding film having high sensitivity and good linearity of pattern can be formed. [Simple diagram description] None [Main component symbol description] None

28

Claims (1)

200819913 X. Patent application scope: 1. A colored photosensitive resin composition containing a photopolymerizable compound (A), a photopolymerization initiator (3), and a coloring agent (a colored photosensitive resin composition, the light) The polymerizable 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 the polybasic acid anhydride (a-3) is a color-sensitive photosensitive resin composition having at least two benzene rings, wherein the polybasic acid anhydride (a-3) contains the following formula (1). And at least one of the compounds shown in (2), [Chemical Formula 1] 〇〇 29 200819913 ο - one ο a 2 R (2) In the formula, R2 represents a colored alkyl resin composition which may have a substituent having a carbon number of 1 to 10, and a coloring photosensitive resin composition according to the above item 1, wherein the resin The acid value of the resin, the solid content of the resin is KOH 10 gram / gram or more and 150 mg / gram or less. 4. The colored photosensitive resin composition according to claim 1, wherein the resin has a mass average molecular weight of 1000. The colored photosensitive resin composition according to the above aspect of the invention, wherein the photopolymerizable compound (A) contains a monomer having an ethylenically unsaturated group. The coloring photosensitive wax composition according to Item 1, wherein the coloring agent (C) is a black pigment. 30 200819913 VII. Designation of representative drawings: (1) The representative representative of the case is: No (2), this representative figure A simple description of the symbol of the component: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 4