TW200836008A - Alkali soluble resin, process for producing the same, photosensitive resin composition containing the same, cured product, and color filter - Google Patents

Abstract

The present invention provides an alkali soluble resin capable of forming photosensitive resin composition suitable for excellent formation of micro patterns and material for high light-shielding or highly colorful color filter. The present alkali soluble resin is expressed as in general formula (1) which has carboxylic acid reside and polymerized non-saturation group in molecules. In formula (1), R1-R4 represent hydrogen atom, alkyl with carbon number of 1-5, halogen atom and phenyl group respectively; R5 represents hydrogen atom or methyl; X represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, 9,9-ylidene group or direct bond; Y represents 4-valence carboxylic acid reside; G represents substitute group with polymerized dual bonds and carboxylic group as expressed by general formula (2); Z represents substitute group expressed by general formula (3); n represents 1-20. In formula (2), R8 represents aliphatic group with carbon number of 3-6; R6 represents 2-valence alkylidene; R7 represents hydrogen atom or methyl; Z represents the general formula (3); q represents 0 or 1. In formula (3), L represents 2- or 3-valence carboxylic acid reside; P represents 1 or 2.

Description

200836008 IX. Description of the Invention [Technical Field] The present invention relates to an alkali-soluble resin which is cured by irradiation with ultraviolet rays or electron beams, and which is formed by alkali development processing, a method for producing the same, and a method for producing the same A photosensitive resin composition of a soluble resin, more specifically, a photosensitive resin composition suitable for producing a photoresist for a color filter, and an alkali-soluble resin suitable for forming the photosensitive resin composition . [Prior Art] A color liquid crystal display device is a liquid crystal portion and a color filter that control the amount of light transmitted or reflected, and the color filter is usually used in a transparent substrate such as glass or plastic sheet. A black matrix is formed on the surface, and then a different color pattern such as red, green, or blue is sequentially formed in a color pattern such as a strip or a grid. In recent years, color liquid crystal display devices have been used in the fields of liquid crystal televisions, liquid crystal screens, color liquid crystal mobile phones, and the like, and color filters are one of important components that affect the visibility of such color liquid crystal display devices. The size of the pattern varies depending on the use of the color filter and the color, and each of the red, green, and blue pixels is ΙΟΟμιη to 50 μmη or less, and the black matrix is 20 μm to ΙΟμιη. Therefore, the photosensitive resin composition is required to form a pattern by high dimensional accuracy. In general, the photosensitive resin composition for the purpose of use is a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble viscous-6-200836008 mixture resin, and the like, and a photopolymerization initiator. Composition. For example, it is exemplified in the application of a material for a color filter as a material for a color filter, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 213213 (Patent Document 1) or JP-A No. Hei 1-152449 (Patent Document 2). A copolymer of acrylic acid or (meth)acrylic acid vinegar, with maleic anhydride, and other polymerizable monomers as a binder resin. However, in the copolymer disclosed herein, since these are random copolymers, an alkali dissolution rate distribution occurs in the light-irradiated portion or the light-unirradiated portion, the range of development operation is narrow, and it is difficult to obtain an acute angle. The shape of the figure or the fine pattern. In particular, when a pigment having a high concentration is contained, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained. Japanese Patent Publication No. 4-340965 (Patent Document 3) discloses an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule, and a negative type in forming a color filter or the like. Valid when the pattern is used. Since the alkali-soluble molecule is insolubilized by light irradiation, it is predicted to have higher sensitivity when compared with the above-mentioned combination binder resin and polyfunctional polymerizable monomer, but the compound exemplified herein is a phenol oligomer. In the case where the polymerizable unsaturated group-containing acrylic acid and an acid anhydride are arbitrarily added to the hydroxyl group, in the proposal, the alkali dissolution rate is widely distributed due to the non-uniformity of the molecular composition, and it is difficult to form a fine negative pattern. Japanese Patent Publication No. 4-345673 (Patent Document 4), JP-A-4-345608 (Patent Document 5), and Japanese Patent Publication No. Hei 4-3 5 545 0 (Patent Document 6) 4-3 63 3 1 (Patent Document 7) discloses a liquid resin using a reaction product of an epoxy group (meth) acrylate having a bisphenol fluorene structure and an acid anhydride. However, the resin 200836008 exemplified by the above is a reaction product of an epoxy (meth) acrylate and an acid anhydride, so that the molecular weight is small. For this reason, the sensitivity of the compound is low, and it is not possible to form a fine pattern. In addition, Japanese Laid-Open Patent Publication No. Hei No. Hei 5-3 3 3 5 5 (Patent Document 8) and JP-A No. 5 - 1 46 1 3 2 (Patent Document 9) And the W094/0080 manual No. 1 (Patent Document 10) discloses an alkali-developing unsaturated resin composition by copolymerizing a dihydroxypropyl acrylate compound and an acid dianhydride, or by using an acid anhydride and A base-developing unsaturated resin composition in which an acid dianhydride and a dihydroxypropyl acrylate compound are copolymerized. At this time, an acid dianhydride and a dihydroxypropyl acrylate compound were copolymerized to obtain an oligomer. However, since the number of polymerizable unsaturated bonds in the repeating unit is constant, the crosslink density cannot be improved, and it is difficult to form a fine line pattern under a high concentration of pigment, and there is a need for improvement. In the Japanese Patent Publication No. 9-3 25494 (Patent Document 1), the molecular weight of the carboxyl group-containing copolymer is increased, and the alkali-soluble resin composition is polyfunctionalized. However, in this case, as in the above-mentioned patent documents, since the number of polymerizable unsaturated bonds in the repeating unit is constant, the crosslinking density cannot be increased. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. [Patent Document 9] Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei 5 - 1 46 1 3 2 [Patent Document 1] W094/00801 Manual [Patent Document 11] In the case of solving the problem of the conventional photosensitive resin composition as described above, the inventors of the present invention have further intensively studied and found that the polymerizable unsaturated group is contained. The carboxyl group-containing copolymer obtained by reacting a diol compound with an acid dianhydride is reacted with an epoxy compound containing a polymerizable unsaturated bond group, and then reacted with an acid anhydride to obtain a composition suitable for forming a photosensitive resin. Alkali soluble resin. Next, by using the alkali-soluble resin, the solubility in the alkali developing solution can be controlled, the crosslinking density can be increased, and the difference in solubility between the hardened portion and the uncured portion to the alkali developing solution can be increased, and a perfect thin line pattern can be formed. The present invention has been completed by producing a photosensitive resin composition having a wide range of development and adhesion in a high density. Therefore, the object of the present invention is to provide a photosensitive resin composition which is excellent in formation of a fine pattern, which is suitable as a material for a high light-shielding or high-color color filter, and an alkali-soluble resin which forms the photosensitive resin composition. Further, another object of the present invention is to provide a film (cured material) and a color filter formed using the above-described high-sensitivity photosensitive resin composition. Further, another object of the present invention is to provide a fine pattern which is excellent in formation even when a local concentration of a light-shielding pigment is added, and is suitable as a black matrix material for a high light-shielding or high-color color filter of -9 - 200836008. A photosensitive resin composition for a black matrix. In other words, the alkali-soluble resin of the present invention is characterized in that it has a carboxylic acid residue and a polymerizable unsaturated group in the molecule as shown by the following general formula (1).

(wherein, Ri, r2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; R5 represents a hydrogen atom or a methyl group; and X represents -CO-, - S〇2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -0, 9,9-indenylene or straight bond; Y system The tetravalent carboxylic acid residue is represented; the G system represents a substituent having a polymerizable double bond and a carboxyl group represented by the general formula (2); the Z system represents a substituent represented by the general formula (3); and the η system represents 1 to 20) -10- 200836008 【化2】 R8—0_{"R6-0 ο—ζ

(wherein R8 represents an aliphatic hydrocarbon group having 3 to 6 carbon atoms; R6 represents a divalent alkylene group; R7 represents a hydrogen atom or a methyl group; Z represents the same as general formula (3); and q represents 0. Or 1 number)

P - co2h (3) (wherein L represents a 2 or a trivalent carboxylic acid residue; P represents 1 or 2) Further, the present invention contains at least (i) the above alkali-soluble resin, (Π) at least A photopolymerizable monomer having one or more ethylenically unsaturated bonds, and (iii) a photopolymerization initiator is a photosensitive resin composition of an essential component. In addition, the present invention is a cured product obtained by curing the photosensitive resin composition, and a color filter formed by coating and curing the cured resin composition. Further, the method for producing an alkali-soluble resin of the present invention is characterized in that a carboxyl group-containing reactant obtained by reacting a diol compound (A) containing a polymerizable unsaturated group with an acid dianhydride (B), and at least An oxirane compound (c) containing one or more poly-11 - 200836008 conjugated double bonds and containing one oxirane ring is reacted to obtain a reactant having a hydroxyl group', and then the hydroxyl group is obtained The reactant is reacted with an acid anhydride (D). In addition, the photosensitive resin composition for a black matrix of the present invention is characterized by containing (i) an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (1). ' 【化4】

(wherein, Ri, R2, R3, and R4 independently represent a hydrogen atom, a carbon number of 1 to 5, a halogen atom or a radical, and represent a hydrogen atom or a methyl group; X system C(CH3)2-, -0-, 9,9-indenylene or a straight bond; Y represents a tetravalent carboxylic acid residue; G represents a substituent having a polymerizable double bond and a carboxyl group; and Z is represented by a general formula (3) Substituents shown; η is a number from 1 to 20) -12- 200836008 [Chemical 5]

C~L—fC02H

\ JV (3) (wherein L represents a 2 or a trivalent carboxylic acid residue; P represents 1 or 2) (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond (iii) A photopolymerization initiator and (W) a light-shielding pigment are essential components. In the following, the present invention will be described in detail. The photosensitive resin composition of the present invention (including a photosensitive resin composition for a black matrix, which is also the same as the following is not particularly limited), and has an alkali-soluble resin represented by the general formula (1) as a main component. A resin composition of a nature of a component of an alkali-developing photosensitive resin composition. Since the alkali-soluble resin represented by the general formula (1) has a photopolymerizable unsaturated group derived from a diol compound having (meth)acrylic acid, it has a radical polymerizability and contains an acid anhydride and an acid The acid group of the anhydride has alkali solubility. The alkali-soluble resin of the general formula (1) is a polymerizable unsaturated group obtained by reacting an epoxy compound having two glycidyl ether groups derived from a bisphenol with (meth)acrylic acid. a reaction product obtained by reacting a diol compound (A) and a tetracarboxylic acid or an acid dianhydride (B) thereof, and reacting with an oxirane compound (C) containing a poly-bond of a poly--13-200836008, and then a carboxyl group-containing interactive copolymer obtained by reacting with a dicarboxylic acid or an anhydride (D) thereof. Since the alkali-soluble resin of the general formula (1) has both a polymerizable unsaturated double bond and a carboxyl group, the alkali-developing photosensitive resin composition has excellent photocurability, excellent developability, and pattern characteristics. Moreover, the physical properties of the protective film, the light shielding film, the red, green, and blue pixels can be improved. The method for producing the soluble resin shown by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) is an epoxy compound having two epoxidoether groups derived from bisphenols, and particularly preferably an epoxy represented by the general formula (4). The polymerizable unsaturated group-containing diol compound (A) obtained by reacting a compound with (meth)acrylic acid is derived. 【化6】

In the above general formula (4), R!, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; preferably a hydrogen atom or a carbon number of 1~ An alkyl group of 5 or a phenyl group; more preferably a hydrogen atom. Moreover, the X system represents -(:0-, -8〇2-, -<:(€?3)2-, -81(<:1^3)2-, -(:1^-, - C(CH3)2-, -〇-, 9,9-indenylene or a straight bond, preferably a 9,9-anthracene group. Here, the '9,9-anthracene group means the following general formula (5) The base shown. -14- 200836008 [Chem. 7]

The reaction of the epoxy compound with (meth)acrylic acid can be carried out by a conventional method, for example, using about 2 moles of (meth)acrylic acid for a 1 molar epoxy compound. The reactant obtained by this reaction is described, for example, in Patent Document 6 above. The reaction product obtained by the reaction is a diol compound (A) containing a polymerizable unsaturated group, and an epoxy (meth) acrylate compound represented by the following general formula (6). 【化8】

Preferred bisphenols of the alkali-soluble resin of the general formula (1) are provided, for example, those described below. For example, bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis (4- Hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl)hexa Fluoropropane, bis(4-hydroxy-3,5-dimethylphenyl-15-200836008) hexaoxypropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4- Hydroxyphenyl) dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4·hydroxy-3,5·dichlorophenyl)dimethyl decane, Bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-dual ( 4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5.dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane , 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, double (4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, etc. . Moreover, X is 9,9-arylene, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-double (4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-brominated phenyl)anthracene, 9,9·bis(4-hydroxy-3-fluorinated phenyl)芴, 9,9-bis(4-hydroxy-3,5·dimethylphenyl)anthracene, 9,9-bis(4·hydroxy-3,5-dichlorophenyl)anthracene, 9,9-double (4-Hydroxy-3,5-dibromophenyl)anthracene or the like is preferred. Further, for example, 4,4'-bisphenol, 3,3'-bisphenol or the like is preferable. The alkali-soluble resin of the general formula (1) can be obtained from an epoxy compound derived from the above bisphenols, and includes, in addition to the epoxy compound, a phenol novolak type epoxy compound or a cresol novolak type ring. A compound having two glycidyl ether groups such as an oxygen compound may be used. Further, when the bisphenol is subjected to glycidyl etherification, an oligomer unit represented by the following general formula (7) is mixed, and the average enthalpy of m in the general formula (7) is 〇10, preferably When the range is 〇~2, the performance of the resin composition is not problematic. -16 - 200836008 [Chemical 9]

Next, the production of a diol compound containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride thereof, an oxirane compound containing a polymerizable unsaturated group, and a dicarboxylic acid or an anhydride thereof will be described. A method of the alkali-soluble resin of the present invention represented by the general formula (1). An example of the production method of the alkali-soluble resin of the present invention is shown in the following reaction formula (1). -17- 200836008 【化1 0】

Reaction formula I

-18- 200836008 (wherein R, R2, R3, R4, R5, χ, γ, and g are the same as in the above general formula (1). And 'R6 represents a divalent alkylene group; and R7 represents hydrogen Atom or a methyl group; Z system represents a substituent represented by the general formula (3). Further, ^ represents a number from 1 to 20, ρ is the same as in the general formula (3), and q represents 〇 or 1 Number). In the above reaction formula (I), the epoxy group (meth) acrylate compound of the above general formula (6) obtained by first reacting the above epoxy compound with (meth)acrylic acid [containing a polymerizable unsaturated group The alcohol compound (A)] is reacted with an acid component to obtain a compound represented by the general formula (8) [reactant having a carboxyl group]. In this case, the reaction conditions of the solvent, the catalyst, and the like used are not particularly limited, and are described in detail in the above-mentioned Patent Document 1 and the like. Further, as the acid component, a tetracarboxylic dianhydride (B) obtained by reacting a hydroxyl group in a molecule of an epoxy (meth) acrylate compound can also be used. The acid component has an effect whether it is saturated or unsaturated. Among them, as the tetracarboxylic dianhydride (B), an acid dianhydride of a saturated linear hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, an acid dianhydride of an aromatic tetracarboxylic acid, or the like can be used. Here, the acid dianhydride of a saturated linear hydrocarbon tetracarboxylic acid, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, acid dianhydride of hexane tetracarboxylic acid, or the like, may be substituted with a saturated cyclic hydrocarbon. Saturated cyclic tetracarboxylic acid dianhydride. Further, an acid dianhydride of an alicyclic tetracarboxylic acid such as a cyclobutane tetracarboxylic acid, a cyclopentane tetracarboxylic acid, a cyclohexanetetracarboxylic acid, a cycloheptanetetracarboxylic acid, or an acid of a raw spinel tetracarboxylic acid An anhydride or the like may be an acid dianhydride of an alicyclic tetracarboxylic acid in which a saturated hydrocarbon is substituted. Further, an acid dianhydride of an aromatic tetracarboxylic acid such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl-19-200836008-based tetracarboxylic acid Acid dianhydride and the like. The acid dianhydride of the present invention is preferably an acid dianhydride of biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid or diphenyl ether tetracarboxylic acid, more preferably biphenyltetracarboxylic acid or diphenyl ether tetracarboxylic acid. Acid dianhydride. These acid dianhydrides can also be used in two or more types. The method for producing a compound represented by the general formula (8) by reacting an epoxy group (meth) acrylate compound with an acid component is not particularly limited. The conventional method described in the above Patent Document 1 can be employed. Preferably, the diol compound (A) having a polymerizable unsaturated group represented by the general formula (6) and the dianhydride of the acid dianhydride (B) are obtained by using a terminal of the compound represented by the general formula (8) as a hydroxyl group. The ratio [[B)/(A)] is 50 旲% or more and less than 1 〇〇 mol%, and the reaction is quantitatively carried out. When the molar ratio is less than 50 mol%, the content of the unreacted epoxy group (meth) acrylate compound may increase, and the stability of the alkali-soluble resin composition may decrease. In addition, when the molar ratio is 1% or more, it is feared that the terminal of the compound represented by the general formula (8) will become an acid anhydride, and the content of the unreacted acid dianhydride will increase, and the subsequent ring will be increased. The side reaction occurs when the oxyethane compound undergoes a reaction. Further, the reaction temperature is uniformly dissolved and reacted by adding a raw material at 90 to 130 ° C, and then the reaction is carried out at 40 to 80 ° C and ripening is preferred. Then, the compound represented by the above formula (8) and the oxirane compound (C) are reacted to obtain a compound represented by the general formula (9) [reactant having a hydroxyl group]. The oxirane compound is a compound containing one or more polymerizable double bonds and containing one oxirane ring, such as a glycidyl (meth) acrylate or a 4-hydroxybutyl (meth) acrylate. Ester glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like. -20-200836008 There is no particular limitation on the method for producing the compound represented by the general formula (9), and general reaction conditions in the case of addition reaction of a carboxylic acid and an epoxy compound can be used. Further, a method of producing an epoxy (meth) acrylate compound by reacting an epoxy compound with (meth)acrylic acid described in Patent Document 1 above can be referred to. The compound represented by the general formula (9) is preferably subjected to a reaction temperature at the time of synthesis, preferably in the range of from 40 to 120 ° C, more preferably from 40 to 90 ° C. When the compound represented by the general formula (9) is synthesized, the molar ratio of the oxirane compound (C) to the acid dianhydride (B) used in the reaction of the compound represented by the above general formula (8) is employed. In terms of Moh ratio [(〇/(B)], 160~220 mol% is preferred. When the molar ratio is less than 160 mol%, since the portion is derived from the unreacted carboxylic acid When the ester bond of the acid dianhydride in the compound of the formula (9) forms a half ester, the molecular weight may be lowered due to the regeneration reaction of the acid anhydride. In addition, when the molar ratio is more than 220 mol%, the possibility may be caused. The side reaction or the like from the unreacted oxirane compound causes a change with time of the alkali-soluble resin represented by the general formula (1). Then, the hydroxyl group and the acid anhydride of the compound represented by the above general formula (9) are obtained ( D) The reaction is carried out to obtain an alkali-soluble resin represented by the general formula (10). Here, the acid anhydride (D) may be an anhydride of a saturated linear hydrocarbon dicarboxylic acid or an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid, or aromatic. An acid anhydride of a dicarboxylic acid, etc. Among them, an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid or the like can be used. Anhydride of a chain hydrocarbon dicarboxylic acid such as succinic acid, acetyl succinic acid, adipic acid, sebacic acid, citraconic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, glycol An acid anhydride, azelaic acid, suberic acid, diethylene glycol acid or the like, or a hydrocarbon-substituted linear hydrocarbon dicarboxylic anhydride. Further, saturated cyclic-21 - 200836008 hydrocarbon dicarboxylic acid An acid anhydride such as an acid anhydride such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, raw spinane dicarboxylic acid or hexahydro trimellitic acid, or a saturated hydrocarbon substituted aliphatic ester. An anhydride of a cyclic dicarboxylic acid. Further, an anhydride of an unsaturated dicarboxylic acid such as maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl ortho-methylenetetrahydrophthalic acid, or hexachloro An anhydride of endo-alkylene-tetrahydrophthalic acid or trimellitic acid. Among these, the preferred anhydride (D) is succinic acid, itaconic acid, tetrahydrophthalic acid, and hexahydro-bias. An anhydride of trimellitic acid, phthalic acid or trimellitic acid, more preferably an anhydride of succinic acid, itaconic acid or tetrahydrophthalic acid. The alkali-soluble resin shown in (10) is not limited to an example of the alkali-soluble resin represented by the general formula (1). The reaction of the hydroxyl group of the compound represented by the general formula (9) with the acid anhydride (D) is made in general. The reaction temperature at the time of synthesizing the compound represented by the formula (10) is preferably in the range of 20 to 120 ° C, more preferably 40 to 90 ° C. The acid anhydride obtained by synthesizing the compound represented by the general formula (10) ( The molar ratio of D) can also be converted into the molar number (mol) of the diol compound (A) having the polymerizable unsaturated group, the acid dianhydride (B), and the oxirane compound (C). For the formula (2x((A)-(B)) + (C))), that is, the molar ratio [(D)/{2[(A)-(B) + (C)]}] is 20~ 110 mol%. The molar ratio of the anhydride is arbitrarily changed within the above range for the purpose of adjusting the acid bismuth of the alkali-soluble resin represented by the above general formula (1). For the example of the method for producing the general formula (1), when 9,9-bis(4-hydroxyphenyl)fluorene is used as a starting material, the specific examples are as follows. First, 'react 9,9-bis(4-hydroxyphenyl)anthracene with epichlorohydrin' to synthesize bisphenol oxime type epoxy compound represented by the following general formula (!), -22-200836008, and The bisphenol fluorene type epoxy compound is reacted with (meth)acrylic acid represented by CH2=CHR5-COOH (R5 is the same as the above) to give a bisphenol fluorene type epoxy represented by the following general formula (12). Synthesis of a base (meth) acrylate resin. Then, the bisphenol fluorene type epoxy (meth) acrylate resin is heated in a solvent such as propylene glycol monomethyl ether acetate to obtain an acid dianhydride (B), an oxirane compound (C), The acid anhydride (D) is sequentially reacted to obtain an alkali-soluble resin of the above general formula (1). [1 1]

Further, the photosensitive resin composition of the present invention contains the alkali-soluble resin of the above general formula (1) as a main component of the resin component. Here, the resin component means a component which forms a resin by polymerization or hardening, and may contain an oligomer or a monomer in addition to the resin. Further, when the main component is contained, the alkali-soluble resin of the general formula (1) is contained in the resin component in an amount of 30% by weight or more, -23 to 200836008, preferably 50% by weight or more, more preferably 6% by weight or more. The photosensitive resin composition of the present invention may further contain an alkali-soluble resin represented by the general formula (1) as an essential component, and the component other than the resin of the general formula (1) may be a resin component or a solvent or a hydrazine. A non-resin component such as a filling material or a coloring agent. In order to produce a characteristic as a photosensitive resin composition, it is preferred to contain the following components (1) to (iii) as essential components. In other words, it contains (1) an alkali-soluble resin represented by the above general formula (1), (ii) a photopolymerizable monomer having at least one or more ethylenically unsaturated bonds, and (iii) a photopolymerization initiator as an essential component. . Further, the photosensitive resin composition for a black matrix of the present invention contains the following components (i), (Π), (iii) and (iv) as essential components. In other words, it contains (i) an alkali-soluble resin having a carboxylic acid group and a polymerizable unsaturated group in one molecule as shown in the general formula (1), and (ii) light having at least one or more ethylenically unsaturated bonds. A polymerizable monomer, (iii) a photopolymerization initiator, and (iv) a light-shielding pigment are essential components. Wherein (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond of a component, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 a monomer having a hydroxyl group such as ethylhexyl (meth)acrylic acid, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylene glycol di(meth)acrylic acid Ester, tetraethylene glycol di(meth)acrylate, tetramethyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tris(methyl) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tris(meth)acrylate-24-200836008 ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(methyl) a (meth) acrylate such as acrylate or glycerol (meth) acrylate. These compounds may be used alone or in combination of two or more. The ratio of the components (ii) to (i) the alkali-soluble resin represented by the general formula (1) [(i)/(ii)] is preferably 20/8 0 to 90/10, preferably It is 40/60~8 0/20. When the blending ratio of the alkali-soluble resin is small, the cured product after photohardening becomes brittle, and since the acid enthalpy of the film on the unexposed portion is low, the solubility of the alkali developing solution is lowered and the pattern boundary is not conspicuous. The problem arises. On the other hand, when the blending ratio of the alkali-soluble resin is larger than the above range, when the proportion of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and the acid enthalpy of the resin component is too high, and the exposed portion is exposed. Since the solubility of the alkali developing solution is high, the pattern formed is thinner than the target line width, and the pattern defect is liable to occur. Further, a photopolymerization initiator of the component (iii) such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichlorobenzene Acetophenones such as ethyl ketone, trichloroacetophenone, p-butyl acetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamino Benzophenones such as benzophenones, benzophenones, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., 2- (o-chlorophenyl)-4,5-phenyldiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)diimidazole, 2-(ortho -fluorinated phenyl)-4,5-diphenyldiimidazole, 2-(o-methoxyphenyl)-4,5-diphenyldiimidazole, 2,4,5-triaryldiimidazole, etc. Diimidazole-based compounds, 2-trimethylmethyl-5-styrene-25-200836008 keto-1,3,4-oxadiazole, 2-trichloromethyl- 5-(p-cyano) Halogenated methyl group of styryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole Thiazole compounds, 2,4,6-para (methyl trichloride)-1,3,5- Pyrazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(methyl chloride)-1,3, 5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4 ,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)·4,6-bis(trichloromethyl)_1,3,5_three Pyrazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl )-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)·1 , a halogenated methyl- 2nd-triazine-based compound such as 3,5-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-1,2·( O-benzhydrylhydrazine), 1-(4-phenylsulfonylphenyl)butane-1,2-dione-2-indole-o-benzoate, 1-(4-methyl Sulfohydroxyphenyl)butane-1,2-dione-2-indole-o-acetate, 1-(4-methylsulfonylphenyl)butan-1-one oxime-o-B O-nonyl fluorene compounds such as acid esters, benzyl dimethyl acetal, thioxanthone, 2-thioxanthone, 2,4-ethyl thioxanthone, 2-methyl a sulfur compound such as thioxanthone or 2-isopropylthioxanthone, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylfluorene or the like Organic peroxides such as anthraquinone, azobisisobutyronitrile, benzammonium peroxide, cumenyl peroxide, 2-mercaptobenzimidazole, 2,mercaptobenzoxazole, 2-anthracene A thiol compound such as a benzothiazole, a tertiary amine such as triethanolamine or triethylamine, or the like. These photopolymerization initiators may be used alone or in combination of two or more. (iii) The amount of the photopolymerization initiator used is 'in terms of the total weight -26-200836008 parts by weight (i) based on the alkali-soluble resin represented by the general formula (1) and (ii) the photopolymerizable monomer. It is preferably 2 to 50 parts by weight, more preferably 15 to 40 parts by weight. When the blending ratio of the photopolymerization initiator of the (Π) component is too small, the photopolymerization rate is slow and the sensitivity is lowered. On the other hand, when there is too much, there is a fear that the sensitivity is too strong, the line width of the pattern becomes too thick for the pattern mask, and the faithful line width cannot be reproduced for the mask, and the pattern boundary is not obvious. problem. Further, the photopolymerization initiator of (iii) may also contain a photo-sensitizer, but may not be added with another photo-sensitizer. Further, the light-shielding pigment of the component (iv) is, for example, a black organic pigment, a mixed organic pigment or a light-shielding material. Among them, black organic pigments such as phenanthrene black, dark blue black, and the like. The mixed color organic pigment is mixed with at least two or more kinds of pigments selected from the group consisting of red, blue, green, purple, dark blue, and magenta, and is similarly blackened. The light-shielding material such as carbon black, chromium oxide, iron oxide, titanium black, nigrosine, and quinoline black can be appropriately selected from two or more types, particularly carbon black, in terms of light blocking property, surface smoothness, dispersion stability, and phase with resin. It is preferred in terms of good solubility. (iv) The light-blocking pigment of the component may be used together with the dispersing agent as needed. The dispersing agent is, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, an anthraquinone system or a fluorine compound. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. (iv) The amount of the light-shielding pigment to be used is 30 to 28 parts by weight, preferably 1 part by weight, based on the alkali-soluble resin represented by the general formula (1) and (ii) the component. It is in the range of 50 to 23 0 parts by weight. When the ratio is less than this, the light-shielding property is insufficient, and in order to obtain a desired light-shielding ratio, the film thickness of -27-200836008 must be thick, and the surface smoothness of the color filter is not easily obtained. On the other hand, when the amount is too large, the dispersion stability of the photosensitive resin composition for the black matrix is lowered, and when the content of the photosensitive resin of the original binder is reduced, the development characteristics are impaired and the film formation function is impaired. The question of seeking. A photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1), a photopolymerizable monomer represented by the formula (1), and a photopolymerization initiator of the component (iii) as an essential component It is extremely useful for materials for color filters such as color filter inks and protective films. Further, the photopolymerizable monomer containing the (i) component, the alkali-soluble resin represented by the general formula (1), the photopolymerizable monomer of the component (ii), the photopolymerization initiator of the component (iii), and the (iv) component are contained. The pigment is a photosensitive resin composition for a black matrix which is an essential component, and is extremely useful as a black matrix material for a color filter. Further, it may be dissolved in a solvent as needed, and may be used in combination with various additives. When the photosensitive resin composition of the present invention is used for a color filter or the like, it is preferred to use a solvent in addition to the above components. The solvent is, for example, an alcohol such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol or propylene glycol, or a terpene such as β-nonenol, acetone, methyl ethyl ketone, cyclohexanone or hydrazine. Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl card Alcohol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. Ethylene glycol such as glycol ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate Ethyl carbitol -28- 200836008 Acetate such as acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., by using Dissolved and mixed to form a uniform solution-like composition. Further, in the photosensitive resin composition of the present invention, an additive such as a curing accelerator, a thermal polymerization inhibiting agent, a plasticizer, a chelating material, a solvent, a leveling agent, an antifoaming agent or the like may be blended as needed. Among them, thermal polymerization inhibiting agents are, for example, hydroquinone, hydroquinone monomethyl ether, pyrophenol, -3-butylcatechol, phenothiazine and the like. Plasticizers such as dibutyl phthalate, dioctyl phthalate, cresol and the like. A chelating material such as graphite rod, cerium oxide, mica, alumina, or the like. Further, the antifoaming agent or the leveling agent is, for example, a lanthanide, fluorine-based or acrylic compound. In the photosensitive resin composition of the present invention, the solid content other than the solvent (the solid portion includes the monomer which forms a solid component after curing) is contained in a total amount of 70% by weight or more (preferably 80% by weight or more, more preferably (90% by weight or more) of the alkali-soluble resin, (Π) photopolymerizable monomer, and (iii) photopolymerization initiator represented by the general formula (1), and (iv) a light-shielding pigment added as required should. The amount of the solvent varies depending on the viscosity of the target, and is preferably in the range of 20 to 80% by weight based on the total amount. When the photosensitive resin composition of the present invention is used as a color filter, it is suitable for use as a protective film and a black matrix. The film (cured material) of the present invention is dried by, for example, coating a solution of the photosensitive resin composition on a substrate, and irradiating light (including ultraviolet rays, radiation, etc.) to cure the material. When the portion irradiated with light and the portion not irradiated with light are provided, only the portion irradiated with light is hardened, and when other portions are dissolved in an alkali solution, a desired pattern can be obtained. -29-200836008 Next, the use sensitivity is explained. A method of producing a color filter of a resin composition. First, after coating the photosensitive resin composition on the surface of the substrate, a prebaking treatment is performed to evaporate the solvent to form a film. Then, after exposure to the film through a mask, development is performed using an alkaline developing solution, and the unexposed portion of the film is dissolved and removed, and then the portion where the pixel is formed by the post-baking process is drawn. The black matrix formed. On the substrate, for example, a liquid composition in which a photosensitive resin composition of a red pigment is dispersed is applied, and then prebaked to evaporate the solvent to form a film. Then, after exposure to the film through the mask, development is performed using an alkaline developing solution, and the unexposed portion of the film is dissolved and removed, and then post-baking treatment is performed to form red in a predetermined arrangement. The prime picture of the pictogram. Then, using a liquid composition of a photosensitive resin composition in which a green or blue pigment is dispersed, coating, prebaking, exposure, development, and post-baking of each liquid composition are carried out in the same manner as described above. In the process, a green pixel sequence and a blue pixel sequence are sequentially formed on the same substrate, and a pixel sequence of three primary colors such as red, green, and blue is disposed on the substrate, and each liquid composition is performed thereon in the same manner as described above. The coating, prebaking, exposure, development, and post-baking treatment are used as a protective film to obtain a color filter formed with a protective film. When the photosensitive resin composition is coated on the substrate, any method such as a roll coating machine, a flash coating machine or a rotary machine may be employed in addition to the conventional solution dipping method and spraying method. After the desired thickness is coated by such a method, the solvent is removed (prebaking treatment) to form a film. The prebaking is carried out by heating, vacuum drying or a combination of an oven, a hot plate or the like. Pre--30- 200836008 The heating temperature and heating time of the baking treatment are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 120 ° C for 1 to 10 minutes. For the radiation used for producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength of 250 to 45 Onm is preferable. Further, a developing solution suitable for the alkali development treatment, for example, an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, or the like, in particular, 0.05 to 10% by weight of sodium carbonate and carbonic acid may be used. A weakly alkaline aqueous solution of a carbonate such as potassium or lithium carbonate is preferably imaged at a temperature of 20 to 30 ° C, and a fine image is precisely formed using a commercially available developing machine or an ultrasonic cleaner. Further, after the alkali development treatment, water washing is usually carried out. As the development processing method, a rinsing development method, a spray development method, an immersion development method, a foaming (liquid) development method, or the like can be used. The image forming conditions are preferably 1 Torr to 120 seconds at normal temperature. After the development, heat treatment (post-baking treatment) was carried out at a temperature of 180 to 0.25 ° C and for 20 to 100 minutes. This post-baking treatment is carried out for the purpose of improving the adhesion between the patterned film and the substrate. This is carried out by heating in an oven, a hot plate or the like in the same manner as the prebaking treatment. The patterned film of the present invention is formed by the above-described lithography through various processes. A substrate used for forming a color filter having a pixel and/or a black matrix, such as glass, a transparent film (e.g., polycarbonate, polyethylene terephthalate, polyether oxime, etc.). Further, depending on the necessity, a transparent electrode layer, a drug treatment by a decane coupling agent, a plasma treatment, an ion thin layer coating treatment, a sputtering treatment, a gas phase reaction method, and a vacuum evaporation may be carried out -31 - 200836008 Proper pre-processing such as processing. [Effect of the Invention] The photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1). When compared with a conventional one, the solubility in the alkali developing solution is high, and The number of ethylenically unsaturated bond groups in one molecule is large, so the crosslink density after hardening is high. In other words, since the hardened portion and the uncured portion after irradiation with ultraviolet rays or electron beams have a large difference in solubility with respect to the alkali developing solution, a fine pattern can be formed even when the film or the high colorant concentration is used. Therefore, the photosensitive resin composition of the present invention is suitable for forming a color filter, and is particularly suitable as a color filter protective film material and a material for forming a black matrix. Further, the obtained color filter is extremely useful, for example, in a transmissive, reflective or transflective color liquid crystal display device, a color photographic tube element, a color sensor or the like. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail based on examples and comparative examples. Further, the present invention is not limited by the embodiments and the comparative examples. Further, the evaluation of the resin in the following examples was carried out as follows without particular limitation. [Solid concentration] The resin solution obtained in the example (including the comparative example) impregnated with lg in a color filter [Weight: W〇(g)] (including the reaction product or the alkali-soluble-32-200836008 resin) The weight [W1 (g)] was weighed and the weight [W2 (g)] after heating at 16 ° C for 2 hours was obtained by the following formula. Solids concentration (weight 毚 = 1 〇〇 x (Wr w 〇) / ( Wi- Wo) [acid 値] The resin solution was dissolved in dioxane, using phenolphthalein as an indicator, and a 1/10 N-KOH aqueous solution was used. [Molecular weight] Using tetrahydrofuran as a developing solvent, gel permeation chromatography (GPC) was used as a standard polystyrene conversion to obtain a weight average molecular weight (M w). Moreover, in the examples, The abbreviations are as follows: FHPA: Equivalent reactant of bisphenol quinone type epoxy resin and acrylic acid (manufactured by Xinyi Iron Chemical Co., Ltd., ASF-400 solution: solid content concentration 50 wt%, solid content conversion acid 値 1.28 mg KOH / g) FHPPA: bis(phenylphenol) oxime epoxy resin equivalent equivalent of acrylic acid (50wt% PGMEA solution, solid acid equivalent of 7.51 mgKOH/g)

BisA-GEA: equivalent reactant of A diglycidyl ether and acrylic acid (50wt% PGMEA solution, solid acid equivalent of yttrium 1.72mgKOH/g) BDPA: 3,3,,4,4,-biphenyl Carboxylic dianhydride BTDA: 3,3,,4,4,-benzophenone tetraresic acid dianhydride ODPA: 3,3,,4,4'-diphenyltetracarboxylic acid dianhydride-33- 200836008 CHDA: 3,3',4,4, diphenyltetracarboxylic acid dianhydride 1, : 1,2,3,6-tetrahydrophthalic anhydride ΗΗΡΑ: hexahydrophthalic anhydride GMA: methacrylic acid ring Oxypropyl propyl ester HBAGE: 4-hydroxyphenyl acrylate oxime oxime: tetraethylammonium bromide oxime: triphenylphosphine PGMEA: propylene glycol monomethyl ether acetate [Embodiment] [Examples] [Example 1 In a 100 ml ml four-necked flask equipped with a reflux cooler, 600.00 g (0.49 mol) of FHPA [(A) component] 50% PGMEA solution, 72.75 g (0.247 mol) BPDA [(B) component], 3 9.5 6g of PGMEA and 1.30g of TPP, heated at 1 2 0~1 2 5 °C, stirred for 2 hours, and further heated and stirred at 7 0~7 5 °C for 6 hours. The reaction product (a) was obtained. The solid content of the obtained reaction product (a) was 52.4% by weight, the acid bismuth resin (solid content) was 78.0 mgKOH/g, and the weight average molecular weight (Mw) by GPC analysis was 3,400. Then, 73.92 g (0.52 mol) of GM A [(C) component] was added to the reaction product, and the mixture was stirred at 80 ° C for 8 hours to carry out a reaction. Further, 156.71 g (1.03 mol) of THPA [(D component] was poured into the flask, and the mixture was stirred at 8 ° C for 7 hours to synthesize an alkali-soluble resin (1)-. The obtained -34-200836008 alkali-soluble The solid content of the resin was 6 2 · 0 wt %, the acid yttrium (solid content conversion) was 111.8 mg K0H/g, and the Mw by GPC analysis was 3700. Further, the alkali-soluble resin (1)-1 of Synthesis Example 1 was synthesized. The (A) to (D) component names and mixing ratios used, and the obtained alkali-soluble resin (1)-1 lipid weight average molecular weight and acid enthalpy are shown in Table 1 (for the following examples and references) The same applies.) [Example 2] 600.00 g (0.49 mol) FHPA [(A) component] 50% PGMEA solution, 9 6.02 g (0.33) was added to a 100 ml flask equipped with a reflux cooler. Mob) BPDA (component (B)), 4.36 g of PGMEA, and 1.02 g of TEAB, stirred under heating at 1 2 0 to 1 2 5 °C for 2 hours, and at 60 to 65 ° C The reaction product (b) was obtained by heating and stirring for 8 hours. The solid content of the obtained reaction product (b) was 57.8 wt%, and the acid hydrazone (solid content conversion) was 91.6 mgKOH/g, and the weight average molecular weight (Mw) analyzed by GPC was 8 800. Then, 93.82 g (0.66 mol) of GMA [(C) component] was added to the reaction product (b) at 80 The reaction was carried out by stirring for 24 hours at ° C. Further, 1 5 3.67 g (1.01 mol) of THPA [(D component], and 153.67 g of PGMEA was added to the flask, and stirring was carried out at 80 ° C for 24 hours to synthesize a base. Soluble resin (1)-2. The solid content of the obtained alkali-soluble resin was 59.2% by weight, the acid bismuth (calculated as solid content) was 126.8 mgKOH/g, and the Mw by GPC analysis was 6800. -35-200836008 [Implementation Example 3] 200 〇g of the reaction product (b) obtained in the above Example 2 and 13.36 g (0.094 mol) of GMA [(C) component] were placed in a 500-neck flask equipped with a reflux condenser. The mixture was shaken at 80 ° C for 24 hours. In addition, 28.91 g (0.19 mol) of THPA [(D component] and 28.91 g of PGMEA was added to the flask, and stirring was carried out at 80 ° C for 24 hours to synthesize Alkali-soluble resin (1)-3. The solid content of the obtained alkali-soluble resin is 59.2% by weight, and the acid bismuth (in terms of solid content) is 10 mg KOH/g, which is analyzed by GPC. Is 6700. [Example 4] In a 500-neck flask equipped with a reflux cooler, 200 g of the reaction product (b) obtained in the above Example 2 and 27.0 lg (0.19 mol) GMA [(C) component were added. ], stirring at 80 ° C for 24 hours, and adding 12.78 g (0.084 mol) of THPA [(D component] and 12.78 g of PGMEA in the flask, stirring at 80 ° C for 24 hours, synthesis) The alkali-soluble resin (1)_4. The solid-soluble resin obtained had a solid content concentration of 60.5 wt%, acid bismuth (calculated as solid content) of 32.5 mgKOH/g, and Mw of 6400 by GPC analysis. [Example 5~ 1 4 ] At least a part of the components (A) to (D) used in Example 2 are substituted with the raw materials described in Table 1 below, in other words, the raw materials described in Table 2 of FHPA, bpda, THPA or GMA are used. The reaction was carried out in the same manner as in Example 2 except that the reaction was carried out to obtain an alkali-soluble resin (1)-5 to (1,14, -36-200836008 [Example 15] except for the THPA [(D) component of the above Example 1. The reaction was carried out in the same manner as in Example 1 except that the amount of addition was changed to 1 1 8.68 (0.78 mol) to obtain an alkali-soluble resin (1)-15. [Reference Example 1] 500 00 ml of a four-necked flask equipped with a reflux cooler was charged with 206.26 g (0.17 mol) of FHPA in 50% PGMEA solution, 0.08 5 mol BPDA, 0.085 mol THPA, 26.0 g PGMEA, and 0.45 g TPP. 120 ° 1 at 25 ° C under heating and stirring for 6 hours to obtain a resin (reference)-1. The solid content of the obtained alkali-soluble resin was 55.6 wt%, and the acid bismuth (calculated as solid content) was 103.0 mgKOH/g. The Mw analyzed by GPC was 2600. [Reference Example 2] In a 1000 ml four-necked flask equipped with a reflux cooler, 600.00 g (0.49 mol) of FHPA 50% PGMEA solution, 9 6 · 0 2 g (0 · 3 3 Mob) BPDA, 4.36 g of PGMEA, and 1.02 g of TEAB, stirred at 120 to 125 ° C for 2 hours, and heated and stirred at 60 to 65 ° C for 8 hours. (Reference)-2. The solid content of the obtained alkali-soluble resin was 58% by weight, and the acid bismuth (calculated as solid content) was 91.0 mgKOH/g, and the Mw by GPC analysis was 8600. -37-200836008 Ν\\ 1Ν^ ο (N (Ν vn (N mo κη vq Ο m 56.7 inch · oo v〇00 gm painting (Ν Ό Os wn s VO (N VO S ^T) <N Ό CN § § 6.8 126.8 100.3 rn oo o VO cn inch · 00 CN inch · O) o vq 1—Η (N ΡΊ rn 00 Os Os in r—^ 卜卜<Ν ΟΝ vd 00 ss (N Os 1 ^ On ε Mw 3700 6800 6700 6400 8900 8000 8500 8500 9000 9400 9400 7300 7800 7700 6120 2600 8600 έ〇α九1.02/1 Η s S Yinisi«—H rS \ s 1.03/1 s r-^ rn 〇s 1.03/1 S i—H s rH s .1—1 ίη tn 1 Q ω ι—Ι 1~f OT—^ fH d 〇C/B 2.11/1 1 » ·Η (Ν f—^ CN r—H cs H ( N CN 1—^ CS T—^ (NS 2.11/1 Miscellaneous 1 Α/Β 1/0.5 SO 'Ο 岑VO \ov〇VO S VO VO νο ν〇νο νο VO v〇VO VO 1/0.5 tn VO v Ο Ο f—^ oo 5 i—lo 赘H oor—H 〇r—H ο Τ-Η ο r"H oy < oo H o K ffi Η Η κ XXX XXXX Κ ffi X 1 Η HH ffi E ffi Ffi X ffi ffi KHH <<<< PQ 〇 <<<<<<<<<< 2 < s 1 1 α ο ο 〇 PQ X 〇〇ϋ Oo ο ο o 〇〇Β <<<<<<<<<<<<<<<<<<<<<<<<<<><<<>QpLiQ Ρμ Q 0. QQ Oh QX u QH Ph QQ ffi UQHQ ffi UQHQQ Ph Q Ph ffl PQ PQ 0Q PQ 〇PQ Ο PQ 〇PQ PQ 0Q geisha Λ each BisA- GEA <<<< 5: κ Κ E ffi (XK 5: u. Ph K 5: Ρη 5: Ρη c/3 ω S〇CQ 〇X Ph KK Ph rH (Ν m W 4^5 Ϊ VO 卜 00 〇so ¥—Μ (N m ψ· 1 inch τ—H 1—((N series 遝 遝 U U U IK 伽 ( #K u IK * uw {輙Ιϋ u Ιϋ IK 杂 杂 - 38 - 200836008 Next, the present invention will be specifically described based on the examples and comparative examples in the case of producing a color filter. Moreover, the invention is not limited by these. Here, the raw materials and the abbreviations used in the production of the color filters of the examples and the comparative examples are as follows. (1) Ingredients: (1)-1 to (1)-4, (Reference)-1 and (Reference)_2: the alkali-soluble resins obtained in the above Examples 1 to 4 and Reference Examples 1 and 2, (ii) - l Component: dipentaerythritol hexaacrylate (iii) -1 component: oxime ester photopolymerization initiator (Chiba Special Chemicals, 衣鲁卡奇亚(译音)〇XE01) (iii)-2 Ingredients: rice ketone ( Light sensitizer) (V) component: tetramethylbiphenyl type epoxy resin solvent: cellosolve acetate by the above-mentioned compounding ingredients [(1), (ii), (iii) & (v) The photosensitive resin composition of the alkali-soluble resin obtained by using the above Examples 1 to 4 and Reference Examples 2 to 2 was prepared at a ratio shown in Table 2. [Table 2] (1) or (Reference to ( (iiH component (9)-1 component (V) component solvent ratio (weight ratio) 20 8.6 1.2 0.2 4.4 65.6 [Example 1 6 to 1 9 , Comparative Example 1 to 2 ] The photosensitive resin composition using the soluble resin obtained in the above Examples 1 to 4 and Reference Examples 1 to 2 was subjected to post-baking treatment on a glass substrate of -39-200836008 1 2 5 mm x 125 mm using a spin coater. The film was coated at a thickness of 2 μm, and prebaked at 90 ° C for 2 minutes, and then a coated plate was formed. Then, a high-pressure mercury lamp of 500 W/cm 1 was irradiated with a illuminance of 10 m 5 / wavelength of 3 m 5 / via a pattern mask. The photo-hardening reaction of the photosensitive portion was carried out for 10 seconds in the ultraviolet light of cm1. Secondly, the coated plate after the exposure was observed in a 1 wt% aqueous solution of sodium carbonate at 25 ° C, and the image was further observed for 20 seconds. The unexposed portion of the coating was removed by washing with water, and then subjected to heat drying at 203 ° C for 30 minutes using a hot air dryer to obtain a test color filter. Evaluation Example 1 6 to 19 And the color filter of the test color filter of Comparative Examples 1 to 2 In particular, the sample obtained is evaluated for the dryness of the film, the developability of the aqueous solution, the exposure sensitivity, the film hardness, the adhesion to the substrate, the heat resistance, and the chemical resistance. The physical property data were measured under the following conditions: (1) The dryness of the film of the film was evaluated based on JIS-K5400. The evaluation criteria are as follows: 〇: All wrinkles are not △ :Slightly wrinkled person X: Significant wrinkles 1 Imaging effect on aqueous alkali solution After patterning in 1% by weight sodium carbonate aqueous solution at 15 °C, dip-40-200836008 Stains 2 0 The image was developed in seconds, and the resin remaining 40 times was visually evaluated. The evaluation criteria are as follows: 〇: Those with good imageability (no photoresist residue on the glass) △: The development is slightly different Good (slightly resistive residue on the glass) X: Poor image (some photoresist residue on the glass) (3) Exposure sensitivity makes the exposure mask with 1 〇μπι thin line pattern adhered to the film On, use 500W high pressure mercury lamp to l The amount of light was irradiated with 〇J/cm2. Then, in the aqueous solution of 1% by weight of the aqueous alkali solution, the pattern development was carried out at 25 t, and then immersed for 20 seconds to carry out development processing. The line width of the thin line pattern formed is evaluated (the evaluation method is based on the line width pre-thickness when the high sensitivity is higher). (4) After the exposure film is developed, the film is heated at 23 ° C for 30 minutes. The hardness of the coating was expressed by the test method of JIS-K5400. When a load of 1 kg was applied using a pencil hardness tester, the hardness of the film was not scratched. The pencil used is "Mitsubishi High Unit". (5) Adhesion to the substrate After exposure development, at least 100 checkerboards are formed on the film heated at 230 °C for 30 minutes for cross-cutting 'then' using a tape (registered trademark) for peeling test' The peeling of the checkerboard grid was visually evaluated -41 - 200836008 Status. The evaluation criteria are as follows. 〇: All are not peeled off X: There is a little peeling (6) Heat resistance starts after exposure development, and the film is heated at 23 ° C for 30 minutes, and placed in an oven for 3 hours at 25 °C The evaluation of the state of the film is as follows: 〇: There is no abnormality in the appearance of the film X: The appearance of the film is cracked, peeled, and colored (7) Chemical resistance after exposure and development, at 23 ° C The film which was heated for 30 minutes was immersed in the following conditions under the following conditions, and the appearance and adhesion after immersion were evaluated. Acid resistance test: 24-hour alkali resistance test in 5% HC1 1: immersion in 5% NaOH for 24 hours Alkali resistance test 2: 4% KOH, immersed at 50 ° C for 1 minute, alkali resistance test 3: l% NaOH, immersed at 80 ° C for 5 minutes, solvent resistance test 1: NMP, 40 ° C Immersion for 1 minute, solvent resistance test 2: NMP, immersion at 80 ° C for 5 minutes (Note) NMP : N-methyl-pyrrolidone -42 - 200836008 Chemical resistance 〇〇〇〇〇〇 heat resistance 〇〇〇〇 〇〇Adhesive 〇〇<3 〇 XX film hardness inch inch inch inch exposure sensitivity line 10.8 "m 11.0 //m 10.5 β m 11.0//m 9.8 //m 10.1 μνη Imaging 〇〇〇<< X Film Drying Scopolamine Soluble Resin (1)-1 (N rn rH rH (Reference)-1 (Reference)-2 Example 16 Example 实施 Example 18 Example 19 Comparative Example 1 Comparative Example 2 -43- 200836008 From the results of the above Table 3, Example 1 6~ 19. In particular, in the case of the first and sixth embodiments, the photosensitivity and the adhesion are superior to those of the comparative example. In other words, after the ultraviolet or electron beam irradiation, the hardened portion and the uncured portion have a poor solubility to the developing solution. And by increasing the number of ethylenically unsaturated bonding groups in one molecule, it is possible to provide a cured film having good developing properties and high adhesion. Secondly, when manufacturing a black matrix, the examples and comparative examples are used as a reference. The present invention is not limited thereto, and the raw materials and abbreviations used in the production of the black matrix of the following examples and comparative examples are as follows. (i) -1 component: The alkali-soluble resin (i)-2 component obtained in Example 1 was obtained in the above Example 15. The alkali-soluble resin (i) -3 component: the alkali-soluble resin (i) - 4 component obtained in the above Example 2: the alkali-soluble resin (i) - 5 component obtained in the above Reference Example 1: obtained in the above Reference Example 2 Alkali-soluble resin (ii) _2 component: trimethylolpropane triacrylate (iii) -3 component: oxime ester photopolymerization initiator (Chiba Special Chemicals, 衣鲁卡奇亚 OXE02) (iii) -4 Ingredients: benzophenone-based photopolymerization initiator (Chiba Special Chemicals, 衣鲁卡奇亚3 69) (iv) -1 component: pigment concentration 2〇.〇%, total solid content 24% carbon dispersion ( Average particle size 100~130nm) (1 v ) _ 2 component. Pigment concentration 2 〇· 〇%, total solid content 29% carbon dispersion (average particle size 1〇〇~150nm) Solvent-1: propylene glycol monomethyl Ether acetate-44-200836008 Solvent · 2 : cyclohexanone additive-1 : decane coupling agent (SH-6040, manufactured by Toray Raikkinen (transliteration)) The above compounding ingredients were blended in the ratio shown in Table 4 to prepare The photosensitive resin compositions for black photoresist of Examples 20 to 25 and Comparative Examples 3 to 6. Moreover, the numbers in Table 4 are all expressed in parts by weight. [Table 4] Example 20 Example 21 Example 22 Comparative Example 3 Comparative Example 4 (i) Component (1)-1 (1)-2 (i>3 (i)-4 (i)-5 5.68 7.42 5.95 6.23 6.09 (ii) )-l component 0.88 0.88 0.88 0.88 0.88 (iii)-3 Composition 1.76 1.76 1.76 1.76 1.76 (iii)-4 Composition 0.22 0.22 0.22 0.22 0.22 (iv)-l Composition 60.90 60.90 60.90 60.90 60.90 (iv)-2 Ingredients • Discussion - Solvent-1 14.74 13.18 14.48 14.19 14.33 Solvent-2 15.79 15.79 15.79 15.79 15.79 Additive-1 0.03 0.03 0.03 0.03 0.03 Example 23 Example 24 Example 25 Comparative Example 5 Comparative Example 6 (i戚份(1)-2 (i )-2 (1)_2 (i)-4 (1)-4 0.84 1.13 1.45 0.73 1.14 (9)-City 0.96 1.00 1.04 0.94 1.00 (iii)-3 Composition 1.92 1.75 1.57 1.88 1.75 (iii)-4 Composition 0.24 0.20 0.16 0.24 0.20 (iv )-l ingredient • Fine • One - (iv)-2 ingredient 56.00 56.00 56.00 56.00 56.00 Solvent-1 23.94 23.82 23.68 24.11 23.81 Solvent-2 16.00 16.00 16.00 16.00 16.00 Additive-1 0.10 0.10 0.10 0.10 0.10 -45- 200836008 [Implementation Examples 20 to 25 and Comparative Examples 3 to 6] The photosensitive resin composition for black photoresist shown in Table 4 was used. The transfer coating was coated on a glass substrate of 125 mm x l 2 5 mm after the post-baking treatment to a thickness of 0.9 to 1.0 μm, and pre-baked at 80 ° C for 1 minute to form a coated board. The ultraviolet light of a illuminance of 3 nmmJ/Cm2 having a wavelength of 3 65 nm is irradiated with a high-pressure mercury lamp of 50 OW/cm 2 to carry out a photohardening reaction of the photosensitive portion. Secondly, the exposed coated plate is placed in a 0.04 wt% potassium hydroxide aqueous solution or In a 0.5 wt% aqueous sodium carbonate solution, the image was developed by rinsing at 24 ° C to develop a pattern, and then subjected to development treatment for 30 seconds, and then subjected to a spray water washing treatment to remove the unexposed portion of the film. Next, heat drying treatment was carried out at 230 ° C for 30 minutes using a hot air dryer to obtain color filters of Examples 20 to 25 and Comparative Examples 3 to 6. The evaluation results of the color filters of Examples 20 to 25 and Comparative Examples 3 to 6 obtained above, the development properties, the development range, and the like are shown in Table 5. The evaluation methods for this are as follows. Film thickness = Measurement was carried out using a stylus type step shape measuring device (trade name P-10 manufactured by Kenyaluye Dick). Imaging time: The time required to record all patterns when recording alkali, and X when the imaging time is greater than 120 seconds. -46 - 200836008 Thin wire close range: When developing a portion exposed with a 1 Ομπι pattern mask, record the time from when the pattern is seen to when the pattern portion is maintained for 10 ± 1 μm. The line width of the pattern portion was measured using a length measuring microscope (trade name: XD-20, manufactured by Ricoh). Tapered shape: The pattern after development is observed using a scanning electron microscope (trade name VE-780, manufactured by KE YEN CE). The cross-sectional shape of the pattern is maintained as a forward taper, which is a reverse taper. Or X when the peeling condition occurs. Line shape: For the 1 Ομπι line after development, the linearity of the pattern portion or the presence or absence of interference pattern is evaluated by the above-mentioned length measuring microscope. Here, the one with good linearity and no interference pattern is 〇 (good), and those with interference pattern and poor linearity are χ (poor). Only when each item is excellent, the evaluation is ◎. Optical density: Measurement using an optical density meter (manufactured by Otsuka Electronics Co., Ltd.) - 47 - 200836008 ^ J Example 20 Example 21 Example 22 Comparative Example 3 Comparative Example 4 Alkali-soluble resin (i)-l (i)- 2 (i)-3 (i)-4 (i)-5 Film thickness (μηι) 0.9 0.9 0.9 0.9 0.9 Alkaline imaging solution 氤Hg potassium hydride solution ^ Development time (seconds) 32 47 55 89 96 Fine wire adhesion range (sec) 20 30 30 20 30 _ cone shape 〇〇〇 XX line shape 〇〇〇 XX optical density 4.78 4.84 4.75 4.86 4.72 Example 23 Example 24 Example 25 Comparative Example 5 Comparative Example 6 Alkali-soluble resin (i )-2 (i)-2 (i)-2 (i)-4 (i)-4 Film thickness (μηι) 1.0 1.0 1.0 - - One alkali imaging solution Sodium carbonate water g Night imaging time (seconds) 31 31 31 31 31 Thin wire close range (seconds) 40 40 40 Pattern peeling pattern peeling cone shape 〇〇〇 XX line shape 〇〇〇 XX optical density 4.63 4.74 4.84 4.73 4.72 From the results of Table 5 above, the example 20 to 25 color filters, each performance is excellent, especially the black matrix of Example 2 3~2 5 and Comparative Example 5 6 when compared to developing property and is excellent in adhesiveness' reduced even when the amount of the photopolymerization initiator, the fine-line pattern can be formed. In other words, after the ultraviolet or electron beam irradiation, the hardened portion and the uncured portion have a large difference in solubility to the developing liquid, and the number of ethylenically unsaturated bonding groups in one molecule is increased, thereby providing good development and high visibility. Adhesive hardened film. -48-200836008 [Industrial use price 値] When the photosensitive resin composition of the present invention is compared with a conventional one, it has solubility in an alkali developing solution, and is an ethylenically unsaturated bond in one molecule. The number of bases is large, and the crosslink density after hardening is high. In other words, since the difference in solubility between the hardened portion and the uncured portion after the irradiation of ultraviolet rays or electron beams is large, a fine pattern can be formed even if it is a film or a high colorant concentration. Therefore, the photosensitive resin composition of the present invention can be suitably used for various color control inks such as color liquid crystal display devices, color facsimile machines, and image sensors, or color filters for color filters used in optical devices and the like. And a color filter having a black matrix formed by the like, or a display device such as a television, a video recorder, or a computer. In particular, it is suitable as a color filter protective film material and a black matrix forming material. Further, the obtained color filter is extremely useful, for example, in a transmissive, reflective or transflective color liquid crystal display device, a color photographic tube element, a color sensor or the like. -49-

Claims (1)

200836008 X. Patent application scope 1. An alkali-soluble resin characterized by having a carboxylic acid residue and a polymerizable unsaturated group in a molecule as shown in the general formula (1), [Chemical Formula 1] (wherein, Ri, R2, r3, and R4 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; R5 represents a hydrogen atom or a methyl group; and X is a table *-C0- , -S02-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -0-, 9,9-indenylene or a straight bond, Y The structure is not a tetravalent residual acid residue; the G system represents a substituent having a polymerizable double bond and a carboxyl group represented by the general formula (2); the Z system represents a substituent represented by the general formula (3); and the η system represents 1~2 0 number) 【化2】 Wherein R8 represents an aliphatic hydrocarbon group having 3 to 6 carbon atoms; R6 represents a divalent alkylene group; R7 represents a hydrogen atom or a methyl group; and Z represents the same as general formula (3) -50-200836008; q is the number of 〇 or 1) (wherein L represents a 2 or a trivalent carboxylic acid residue; and p represents 1 or 2). 2. The alkali-soluble resin according to claim 1, wherein the diol compound (A) containing a polymerizable unsaturated group and the tetracarboxylic acid or its acid dianhydride (B) are reacted to have a carboxyl group. The reaction product is reacted with an oxirane compound (C) containing at least one polymerizable double bond and containing one oxirane ring to obtain a reactant having a hydroxyl group, and then the base group is obtained. The reaction product is reacted with a dicarboxylic acid or an anhydride thereof (D) to obtain an alkali-soluble resin according to the second aspect of the patent application, wherein when the component (A) and the component (B) are reacted, The molar ratio [(B) / (A )] of the component A) and the component (B) is 50% by mole or more and less than 1% by mole. 4) The alkali-soluble resin of the third aspect of the patent application, wherein the reactants of the component (a) and the component (B) are reacted with the component (c), and the molar ratio of the component (C component) to the component (C) [(C)/(B)] is ι6〇~22〇mol%. 5 ·The alkali-soluble resin of the third item of Shenyang Patent Range, which makes The molar ratio of the [2 (D) component of the reaction (C) component is 2〇~ -51 in terms of (A) to xUA)-(B)] + (C)] · 200836008 1 1 〇 耳 %. A photosensitive resin composition comprising (i) an alkali-soluble resin according to any one of claims 1 to 5, (ii) light having at least one ethylenically unsaturated bond. The polymerizable monomer and (iii) a photopolymerization initiator are essential components. 7. A cured product obtained by hardening a photosensitive resin composition as claimed in claim 6 of the patent application. A color filter characterized by being formed by coating a photosensitive resin composition of the sixth aspect of the patent application and curing the cured product. A method for producing an alkali-soluble resin, which comprises a reactant having a carboxyl group obtained by reacting a diol compound (A) containing a polymerizable unsaturated group with an acid dianhydride (B), and at least 1 One or more oxirane compounds (C) having a polymerizable double bond and containing one oxirane ring are reacted to obtain a reactant having a hydroxyl group, and then 'reacting the reactant having a hydroxyl group with the acid anhydride (D) reaction. A photosensitive resin composition for a black matrix, which comprises (i) an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (1). ' -52- 200836008 【化4】 (wherein, Ri, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; R5 represents a hydrogen atom or a methyl group; and the X system represents -CO-, -S02-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, 9,9-anthracene or straight bond; Y system A tetravalent carboxylic acid residue; g is a substituent having a polymerizable double bond and a carboxyl group; Z is a substituent represented by the general formula (3); and η is a number of 1 to 20) P - G - L - ^ C02H) (3) (wherein L represents a 2 or a trivalent carboxylic acid residue; p represents 1 or 2) (ii) light having at least one ethylenically unsaturated bond A polymerizable monomer, (iii) a photopolymerization initiator, and (iv) a light-shielding pigment are essential components. 1 1 A cured product obtained by hardening a photosensitive resin composition of a black matrix for a black matrix as claimed in claim 10 of the patent application. 1 2. A color filter comprising a cured resin composition for a black matrix which is coated with the black matrix of the first aspect of the patent application, and which is cured by hardening. -54- 200836008 Ming said that there is no simple •• number as the map of the map element: the table pattern represents the book without a set of two or two CC. 8. If there is a chemical formula in this case, please reveal the best display of the characteristics of the invention. Chemical formula: none