TW200949444A - Photosensitive resin and photosensitive resin composition comprising the same - Google Patents

Abstract

Disclosed is a photosensitive resin which can be produced readily at a low cost, is easy to adjust its cross-linking density and acid value and therefore has a wide variety of use applications, has a high sensitivity, and has excellent patterning properties. The photosensitive resin is produced by adding a compound having reactivity to a carboxylic acid and also having an ethylenically unsaturated group to a polymeric compound, wherein the polymeric compound is produced by reacting a compound represented by general formula (1) with a compound represented by general formula (2). [In general formula (1), Y represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a cyclohexyl group, a 9,9-fluorenyl group or a direct bond; R1 and R2 independently represent a hydrogen atom or a methyl group; and n and m independently represent a number of 0 to 4.] [In general formula (2), X represents a tetravalent carboxylic acid residue.]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin and a photosensitive resin composition using the same, and more particularly to a high sensitivity which can be easily manufactured at low cost. In particular, it is used for a photosensitive resin and a photosensitive resin composition which exhibit good pattern properties in negative photolithography etching. Φ [Prior Art] A polymer compound having a radical polymerizable unsaturated bond structure (vinyl group) in a molecule is a photosensitive composition or a thermosetting composition by a crosslinking reaction by polymerization of a vinyl group. Used in a variety of fields. Among them, the photosensitive resin having a bisphenol type aromatic polyester structure in the main chain is excellent in heat resistance and chemical resistance, and thus many proposals have been made so far, and it can be applied to a liquid crystal color filter or a black matrix or a solder resist. Photoresist (Patent Documents 1 to 3). Φ However, any of the photosensitive resins described in these documents is polyesterized with tetrabasic dianhydride after the addition of acrylic acid to the epoxy compound, and the production process is complicated and takes a long time, so that it is manufactured. The cost is high. Further, the properties required for the photoresist are different depending on the application. However, it is difficult to adjust the crosslinking density or the acid value of these photosensitive resins, and thus it is not suitable for a wide range of applications. Further, when it is used for a photoresist, it is difficult to say that the photoresist characteristics such as sensitivity are sufficient. (Patent Document 1) JP-A-2006-276862 (Patent Document 2) JP-A-2006-003860, JP-A-200949444 (Patent Document 3) JP-A No. 9-3 2 5 494 SUMMARY OF THE INVENTION (Disclosure of the Invention) ( In order to solve the problem of the invention, it is an object of the present invention to provide a photosensitive resin which is excellent in sensitivity and can be easily adjusted at a low cost and which can be easily adjusted in crosslink density or acid value. A photosensitive resin and a photosensitive resin composition using the same are provided. (Means for Solving the Problem) In view of the facts, the present inventors have found that a photosensitive resin is obtained by reacting a specific bisphenol with an acid dianhydride in order to solve the above problems and accumulating the results of concentration. The polymer compound obtained by adding a carboxylic acid-reactive compound having an ethylenically unsaturated group can be easily produced at a low cost, and it is easy to adjust the crosslinking density or the acid value, and at the same time, the high-sensitivity patterning property. Excellent, the present invention is completed. In other words, the photosensitive resin of the present invention is obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (2) to have an ethylene property. A saturated carboxylic acid-reactive compound, 200949444 [Chem. 7]

(where Y represents -(:0-, -802-, -(:(€?3)2-, -31((:113)2-, -CH2-, -C(CH3)2-, - 〇-, cyclohexyl, 9,9-fluorenyl or direct bonding, R1, R2 independently represent a hydrogen atom or a methyl group, and n, m independently represent the number of 〇~4)

(2) (wherein X represents a tetravalent carboxylic acid residue). Further, the photosensitive resin composition of the present invention contains the photosensitive resin, a photopolymerization initiator, and/or a photosensitizer. (Effect of the Invention) The photosensitive resin of the present invention is excellent in chemical resistance and heat resistance, has high storage stability, can be easily produced at low cost, is excellent in productivity, and can easily adjust the crosslinking density or the acid value. Suitable for a wide range of applications. Further, the photosensitive resin composition using the photosensitive resin has high sensitivity and good patterning property. (Best Mode for Carrying Out the Invention) The polymer compound constituting the photosensitive resin of the present invention is reacted with a compound represented by the following formula (1) of 200949444 and a compound represented by the following formula (2). The person who got it. 〔化9〕

Where Y represents -(:0-, -802-, -(:(€?3)2-, -31((:>13)2-, -CH2-, -C(CH3)2- , -〇-, cyclohexyl, 9,9-fluorenyl or direct bonding, R1, R2 independently represent a hydrogen atom or a methyl group, and n, m independently represent the number of 0 to 4. The above formula (1) The compound shown (hereinafter sometimes referred to as "compound (1)"), specifically exemplified by bisphenol A, ethoxylated bisphenol A, bisphenol F, ethoxylated bisphenol F, 4, 4 '-biphenol, 3,3'-biphenol, ethoxylated 4,4'-biphenol, ethoxy 3,3'-biphenol, i,l-bis(4-hydroxyphenyl)cyclohexane Alkane, ethoxylated 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxybenzophenone, ethoxylated 4,4'-dihydroxybenzophenone, Bis(4-hydroxyphenyl)fluorene, ethoxylated bis(4-hydroxyphenyl)hydrazine, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, ethoxylated 2,2_bis ( 4-hydroxyphenyl) hexafluoropropane, bis(4-hydroxyphenyl)dimethyl decane, ethoxylated bis(4-hydroxyphenyl)dimethyl decane, 4,4,dihydroxydiphenyl Ether, ethoxylated 4,4'-dihydroxydiphenyl ether, 9,9-double 4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene, etc. The above-mentioned type or two or more types are used. Among them, the Y in the general formula (1) is preferably a 9,9-fluorenyl group. Specifically, it is preferably 9,9-double-8-200949444 (4- Hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis[4.(2-hydroxyethoxy)phenyl]anthracene, most preferably 9 , 9-bis[4-(2-hydroxyethoxy)phenyl]anthracene. Among the compounds (1), the synthesis method of the ethoxylated compound is not particularly limited, and the phenol compound may be added to the epoxy group B. The alkane is synthesized and the ketone or carboxylic acid is added to the phenoxyethanol by the Friedel Craft reaction, but the method of adding the phenoxyethanol has no distribution of the chain length of the ethylene glycol, so it is easy to carry out the physical property. A compound represented by the following formula (2) (hereinafter sometimes referred to as "compound (2)") can be used as the compound which reacts with the above compound (1). [Chemical 1 〇] Ο Ο

(wherein X represents a tetravalent carboxylic acid residue). φ The compound (2) is an acid dianhydride, and specific examples thereof include butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane. Tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, Biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5, 8-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diacetic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3',4,4'- Diphenyl-9-200949444 bismuth tetracarboxylic dianhydride or the like may be used alone or in combination of two or more. A polymer compound obtained by subjecting the compound (2) to an addition reaction in the above compound (1) to form a photosensitive resin of the present invention can be obtained. The ratio of the compound (2) in the addition reaction to the molar ratio of the compound (1) to 1 part by mole is preferably in the range of 110 to 200 mole parts, more preferably 120 to 160 mole parts. When the amount is less than 110 moles, the amount of the carboxylic acid-reactive compound having an ethylenic unsaturated group which contributes to the photosensitivity cannot be increased, and sufficient sensitizing properties may not be obtained. On the other hand, when it exceeds 200 moles, the solubility of the raw material is low, so that it is difficult to synthesize, and the molecular weight required for forming a coating film may not be obtained. A catalyst may also be used when the compound (1) is reacted with the compound (2). The catalyst to be used is not particularly limited as long as it can promote the reaction, and examples thereof include pyridine, quinoline, imidazole, N,N-dimethylcyclohexylamine, triethylamine, and N-methyl. Morpholine, N-ethylmorpholine, triethylenediamine, N,N-dimethylaniline, anthracene, fluorene-dimethylbenzylamine, tris(N,N-dimethylaminomethyl) Phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]nonene-5, etc. a fourth-order ammonium compound such as amine, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or tetramethylammonium hydroxide, tributylphosphine, triphenyl a mixture of phosphines and the like. Further, the amount of the catalyst to be used is not particularly limited, but is preferably in the range of from 1 to 2.0 parts by mass based on 100 parts by mass of the compound (1). When the amount of the catalyst exceeds 2.0 parts by mass, the electrical properties or storage stability of the photosensitive resin may be adversely affected. Further, in the addition reaction, a solvent may be used for the purpose of dissolution of the reaction raw material, reduction of viscosity, and the like. The type of the solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, and ethylene glycol monoethyl. a glycol ether acetate such as ether acetate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, Propylene glycol ethers such as dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Φ acetate, dipropylene glycol monomethyl ether Acetate, propylene glycol ether acetate such as dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid, butyl acetate, etc. Mixtures of esters, dimethyl hydrazine, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like. The amount of the solvent to be used is not particularly limited, but is preferably in the range of 25 to 150 parts by mass based on 100 parts by mass of the total of the compound (1) and the compound (2). When the amount is less than 25 parts by mass, the viscosity is sufficiently lowered. Further, when the amount is more than 150 parts by mass, the concentration of the reactant is too low, and sometimes the reaction rate is lowered. In the above compound (1) and the compound (2), an addition reaction is carried out by adding a solvent or a catalyst as needed, but heating is preferably carried out during the reaction, and the raw material is dissolved by heating, and the reaction rate is also accelerated. The heating temperature can be appropriately set depending on the type of the compound (1) and the compound (2) or the apparatus to be used, but it is preferably in the range of 60 to 220 °C. More preferably in the range of 90 to 160 °C. If the reaction temperature is lower than 60 °C, sometimes it takes time until the end of the reaction. Further, when the reaction temperature is higher than 220 ° C, a side reaction such as coloring or the like is carried out, or the acid anhydride is balanced by a ring closure of -11 - 200949444, and the reaction rate may be lowered.

The polymer compound obtained by the above method is a carboxylic acid-reactive compound having an ethylenically unsaturated group to obtain a photosensitive resin of the present invention. A carboxylic acid-reactive compound having such an ethylenically unsaturated group (hereinafter, simply referred to as a "carboxylic acid-reactive compound") may have an ethylenically unsaturated group, and may easily react with a carboxylic acid. Although it can be used as a limitation, specific examples thereof include an epoxy group having an ethylenically unsaturated group, an isocyanate compound, a vinyl ether compound, a methylol compound, and the like. Specific examples of the epoxy compound include, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinyl benzyl glycidyl ether, and allylic acid. A glycidyl ether, a compound represented by the following formula (4), or the like. [Chemical 1 1] R3

(wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a group represented by the following formula (5)) [Chemical Formula 1]

C2H4〇

C3h6o

C4h8o

(5) (In the formula, r, s, and t each independently represent an integer of 〜1 to 9, but r, s, and t are not equal to each other). The compound represented by the above formula (4) is exemplified by 4-hydroxybutyl (meth) acrylate glycidyl ether, polyethylene glycol-polypropylene glycol ( -12- 200949444 methyl acrylate) glycidyl group. Ether, etc. Specific examples of the isocyanate compound include, for example, 2-(meth)acryloyloxyethyl isocyanate, and specific examples of the vinyl ether compound include 2-(2-vinyloxyethoxy) (meth)acrylate. Examples of the hydroxymethyl compound such as a group include N-methylol (meth) acrylamide and the like. Among these, an epoxy compound is preferable, and a vinylbenzyl glycidyl ether and a 4-hydroxybutyl (meth) acrylate glycidyl ether are particularly preferable. The vinylbenzyl glycidyl ether is a compound represented by the following formula (3), and can improve heat resistance and chemical resistance. 〔化1 3〕

Further, since 4-hydroxybutyl (meth) acrylate glycidyl ether has high sensitivity, it is preferably used. Such a carboxylic acid-reactive compound is subjected to an oxime reaction with the above polymer compound. The ratio of the carboxylic acid-reactive compound in the photosensitive resin of the present invention varies depending on the use, and it is difficult to use it in the case of alkali-developing use, and the acid value of the resin solid content is preferably 30 to 150. The range of mgKOH/g was adjusted. If the acid value is less than 30 KOH/g, the development speed may be lowered to obtain a necessary pattern. Further, when the acid value is higher than 150 mgKOH/g, the image is sometimes excessively developed, the pattern is easily peeled off, and electrical characteristics are also lowered. Further, in the present invention, the acid value of the resin solid content is measured in accordance with JIS-K0070, and in the reaction between the above polymer compound and the decanoic acid-reactive compound, the purpose of promoting the reaction is 13-200949444, and the contact may be used. Media. The type of the catalyst varies depending on the type of the carboxylic acid-reactive compound, and therefore, it is difficult to cite, for example, pyridine, quinoline, imidazole, n, n-dimethylcyclohexylamine, and the like. Triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N,N-dimethylaniline, hydrazine, hydrazine-dimethylbenzylamine, tris(N,N- Dimethylaminomethyl)phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3 .0] an amine of terpene-5 or the like, a fourth-order ammonium compound such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or tetramethylammonium hydroxide; A mixture of tributylphosphine, triphenylphosphine, and the like, and the like. Further, the amount of the catalyst to be used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass based on 1 part by mass of the compound (1). If the amount of the catalyst is too large, it may adversely affect the electrical properties or storage stability of the photosensitive resin. Further, when a carboxylic acid reactive compound is reacted, a polymerization inhibitor is preferably added. If it is a reaction that inhibits the unsaturated bond. The type of the polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, hydroquinone monomethyl ether, tert-butylhydroquinone, tert-butylcatechol, and N-methyl-N-. Nitrosoaniline or N-nitrosophenylhydroxylamine/ammonium salt (made by Wako Pure Chemical Industries, Ltd.: Q-1300), N-nitrosophenylhydroxylamine/aluminum salt (Wako Pure Chemical Industries Co., Ltd.) Preparation: Q-1301), 2,2,6,6-tetramethylhexahydropyridin-1-oxo, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridin-1-oxygen, and the like. Particularly preferred is N-nitrosophenylhydroxylamine/aluminum salt, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo. The amount of the polymerization inhibitor varies depending on the type and the reaction conditions, and therefore it is difficult to achieve the same, but it is preferably in the range of 5 to 200 Å PPm with respect to the entire photosensitive resin. If it is less than this range, the unsaturated bond may react to produce gelation during production, and if it is more than this range, the sensitivity may be lowered, which is not preferable. When the carboxylic acid-reactive compound is added, it is preferred to carry out heating for the purpose of improving the reaction rate. The heating temperature may be appropriately set depending on the type or device of the carboxylic acid reactive compound, but is preferably in the range of about 60 to 150 °C. If the reaction temperature is lower than 60 °C, it sometimes takes time until the end of the reaction. Further, when the reaction temperature is higher than 150 °C, a side reaction such as coloring or a non-saturated bond is caused to cause a gelation.

When the high molecular compound obtained by reacting the above compound (1) with the compound (2) is in the above-mentioned mixing ratio, the compound (2) is excessively compounded with respect to the compound (1)', so that the polymer terminal becomes an acid anhydride structure. Here, when an epoxy group having an ethylenically unsaturated group is used as the carboxylic acid reactive compound, the acid anhydride reacts with the -OH group formed by ring opening of the epoxy ring to cause an increase in molecular weight. When the molecular weight of the reaction is to be inhibited, it is preferred to react a compound having a hydroxyl group represented by the following formula (6) or water at an acid anhydride structure site at the terminal of the polymer. 〔化1 4〕 R5

(wherein R5 represents a hydrogen atom or a methyl group, and R6 represents a group represented by the following formula (7)) -15- 200949444 [Chemical 1 5] ~^-〇2Η40^ ^C3H6〇-j ^C4H8〇- J— (7) (In the formula, i, p, and q respectively represent integers of 〇~9, but 1, p and q are not equal). The reaction may be carried out before the addition of the epoxy group having an ethylenically unsaturated group, or may be carried out simultaneously, but if the reproducibility of the reaction is considered, it is more preferably an epoxy group having an ethylenically unsaturated group. The reaction of the compound is carried out before the reaction. The compound represented by the above formula (6) (hereinafter sometimes referred to as "compound (6)"), specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl) Acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 9-hydroxy decyl (meth) acrylate Among these, from the viewpoint of crosslinking reactivity and cost, it is preferred to use 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate '4-hydroxybutyl acrylate. q A catalyst may also be used in the reaction of the compound (6) or water. The type of the catalyst may be the same as that of the compound (1) and the compound (2), and the user may directly use the reaction, or the same one may be added, or another type of touch may be added. Media. Further, the reaction temperature is preferably in the range of from 60 to 150 °C. If the reaction temperature is too low, it sometimes takes time until the end of the reaction. If the reaction temperature is too high, a side reaction such as coloring or the like may occur, or the reaction may be carried out without a bond to cause gelation. The photosensitive resin prepared by the above-described method is subjected to spray-drying, thin film drying, dipping in a weak solution, reprecipitation, or the like for the purpose of purification, storage, solvent change, etc., to form a solid and take out. Further, the molecular weight of the photosensitive resin of the present invention is not particularly limited to 1,500 to 1,000,000, more preferably 2,000 to 20,000. For this reason, the balance between film strength and development is better. In addition, the molecular weight of the neutral resin in the present specification is a styrene-equivalent weight average molecular weight of GPC according to the conditions described in the examples. φ The photosensitive resin of the present invention contains the above-mentioned photosensitive resin, photoinitiator, and/or A light sensitizer is an essential component. The photopolymerization and/or photo-sensitizer may be mixed or dispersed in a solvent, or chemically bonded to the photosensitive resin. The photopolymerization initiator and/or the photosensitizer # used in the present invention are not limited, but may, for example, be benzophenone or 4-hydroxybenzophenone N,N-dimethylaminobenzophenone. , benzophenone ketone, bis-N,N-diethylaminobiphenyl, 4-methoxy-4,-dimethylaminobenzophenone, etc., 2,4-di Thiol ketones such as ethyl thioxanthone, isopropyl thioxanthone, chlorinone, isopropoxychlorothiazolone, ethyl benzobenzazole, amine hydrazine, chlorine Anthraquinones such as hydrazine, hydrazine-2-sulfate, and 1,2,6-disulfonate, acetophenone benzene, benzoin methyl methacrylate, benzoin phenyl ether, etc. Benzene ethers, 2,4'6-methyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2-(o-chlorophenyl)diphenylimidazole dimer, 2-(o-chloro Phenyl)-4,5-di(m-tolyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl taste polymer, 2-(o-methoxyphenyl) -4,5-diphenylimidazole dimer, agent, but the range of sensitization to obtain a polymerization initiator, no special ttib, bis-ketone, thiothiazepine, I [醌-, benzene-trihalogen-4 , 5-oxygen Pyrazole II 2-( -17- 200949444 p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenyl 2,4,5-triarylimidazole dimers such as imidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, benzyl Dimethyl ketal, 2-benzyl-2-dimethylamino-indole (4-morpholinylphenyl)-butan-1-one, 2-methyl-1-[4-( Methylthio)phenyl]_2_Mallin-1-propene, 2-carbyl-2-methyl-1-phenyl-propyl-1-pyrene, ι_[4-(2-hydroxyethoxy) -phenyl]-2-hydroxy-2-methyl-1-propane_;!-ketone, ;!,2_octanedione, 1-[4-(phenylsulfanyl)-, 2-(o-phenylene)醯基肟)], phenanthrene, 9,10-phenanthrenequinone, methyl benzoin, ethyl benzoin and other benzoin, 9-phenylpyridazine, 1,7-double (9,9' One or two or more of these may be used, such as a pyridazinyl group, a heptazine derivative, or a bis-decylphosphine oxide. Further, an accelerator may be added to the photosensitive resin of the present invention. Examples of the accelerator include, for example, p-dimethylamino benzoic acid ethyl acetonate, p-dimethylamino benzoic acid isoammonium vinegar, N,N-dimethylethanolamine, N-methyldiethanolamine, and the like. Ethanolamine and the like. In the photosensitive resin composition of the present invention, a polymerizable monomer having one or more unsaturated groups in the molecule (hereinafter, simply referred to as "polymerizable monomer") can be further used. Sensitivity, chemical resistance, heat resistance and mechanical strength. Further, a polymerizable monomer may be added for the purpose of adjusting the flow characteristics and the like. When the polymerizable monomer has one or more unsaturated bonds in the molecule, it can be used without particular limitation, and may be appropriately selected according to the intended use and purpose. For example, polyethylene glycol di(meth)acrylate (the number of vinyl groups is 2 to 14), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Trimethylol-18- 200949444 propyl ethoxy tris(meth) acrylate, trimethylolpropane propoxy tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, Tetramethyl methacrylate tetra(meth) acrylate, polypropylene glycol di(meth) acrylate (number of propylene groups 2-14), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, bisphenol A polyoxyethylene di(meth)acrylate, bisphenol a dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate φ, bisphenol A fatty acid of A-oxyethylene di(meth)acrylate, polycarboxylic acid (phthalic anhydride, etc.) and a hydroxyl group and a compound having an ethylenically unsaturated group (hydroxyethyl (meth) acrylate, etc.) (methyl ) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate , (meth)acrylic acid alkyl ester such as 2-ethylhexyl (meth)acrylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether , tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol dihydrate a (meth)acrylic acid addition product of an epoxy compound such as glyceryl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether or glycerol triglycidyl ether, or an unsaturated acid such as maleic acid Organic acids and their anhydrides, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-methylol acrylamide, N-methyl methacrylate Amine, N-ethyl methacrylamide, N-isopropyl methacrylamide, N-methylol methacrylamide, hydrazine, hydrazine-dimethyl methacrylate, hydrazine, hydrazine Ethyl acrylamide, N,N-dimethyl methacrylamide, hydrazine, hydrazine-diethyl methacrylamide, etc. acrylamide -19-200 949444, styrene such as styrene or hydroxystyrene, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole, etc., one of which can be used. Or two or more. In the photosensitive resin composition of the present invention, a coloring agent may be added for the purpose of preventing halo or the like in terms of design, visibility, and photoresist. The type of the coloring agent to be added may be appropriately selected depending on the purpose of coloring, and examples thereof include a phthalocyanine dye, an anthraquinone dye, an azo dye, an indigo dye, a coumarin dye, and a triphenylmethane system. A dye, a phthalocyanine pigment dye, an onion pigment dye, an azo pigment, a quinacridone pigment, a coumarin pigment, a triphenylmethane pigment, or the like can be used. One or two or more. The photosensitive resin composition of the present invention can form a solution or a paste, and therefore may contain a solvent. The type of the solvent to be used is not particularly limited, and examples thereof include ethylene glycol such as water, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and ethylene glycol monomethyl. Glycol ethers such as ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol a glycol ether acetate such as monoethyl ether acetate or diethylene glycol monobutyl ether acetate; propylene glycol such as propylene glycol, dipropylene glycol or tripropylene glycol; propylene glycol monomethyl ether; propylene glycol monoethyl Ethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol ether, propylene glycol monomethyl Propylene glycol ether acetate such as phenyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, -20-200949444 acetone, methyl ethyl ketone, a ketone of methyl isobutyl ketone or cyclohexanone, a lactate such as methyl lactate or ethyl lactate A mixture of acetic acid esters such as ethyl acetate, butyl acetate, etc., dimethyl hydrazine, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like. In the photosensitive resin composition of the present invention, a conventionally known component such as a polymerization inhibitor, a plasticizer, an antifoaming agent, or a coupling agent may be further added as needed. The photosensitive resin composition of the present invention can be obtained by a usual method. The above-mentioned essential components and optional solvents or other optional components are mixed. The photosensitive resin composition of the present invention obtained as described above can be used for a photoresist such as a liquid crystal color filter, a black matrix or a solder resist. When used as a photoresist, the photosensitive resin composition of the present invention forms a solution or a paste and is applied onto a substrate. The coating method is not particularly limited, but may be applied to screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, die coating, and the like. The applied solution or paste is exposed to UV or electron beam by means of a specific mask. When it is applied by using a solvent, it can also be subjected to a drying step. The exposed coating film is developed in a wet manner, and the crucible can be formed into a pattern. The development method may be any of spray type, paddle type, and immersion type, but it is preferably a spray type with few residues. Ultrasonic waves, etc. can also be irradiated as needed. It is advisable to use weakly alkaline water for the developer. An organic solvent, a surfactant, an antifoaming agent, etc. may be added for the purpose of the developmental subsidy. [Embodiment] [Embodiment] - 21 - 200949444 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Example 1 In a 1000 ml flask equipped with a stirrer and a cooling tube, pyromellitic dianhydride (PMDA manufactured by Daicel Co., Ltd.) was placed. 67.5 g, 9,9-bis[4-(2-hydroxyethoxy) Phenyl]anthracene (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF) 82.5 g of propylene glycol monomethyl ether acetate l〇〇g was heated in an oil bath of 155 ° C for 4 hours while stirring under a nitrogen stream. Then, after cooling to 120 ° C, 0.9 g of 4-dimethylaminopyridine was added, and 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo (made by Adeka: Adekastab LA) -7RD) 0.03 g, 20.0 g of 2-hydroxyethyl acrylate, and stirring was continued at 120 ° C for 4 hours. Further, 75.0 g of 4-vinylbenzyl glycidyl ether was added, and the mixture was stirred at 120 ° C for 2 hours. Then, cool to room temperature. Propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 50% by weight to obtain a pale yellow transparent viscous photosensitive resin (A1) solution. The obtained resin solution was measured for viscosity, GPC styrene-equivalent weight average molecular weight, and solid acid value, and the viscosity was 420 mPa · s / 2 5 ° C, and the weight average molecular weight obtained by GPC was 5.330. The solid acid value was 52.0 mgKOH/g. Further, in the viscosity measurement system, a BM type viscometer manufactured by Toki Sangyo Co., Ltd. was used. Further, the measurement of GPC was carried out by using TSKgel G7000HXL, TSKgel GMHXL 2, TSKge 1 G25 00HXL ' by Tosoh Co., Ltd. as a column, and measuring it at a flow rate of 0.5 ml/min with a THF solution of 200949444 at 40 °C. The acid value was measured in accordance with the neutralization titration method of JIS-K0070. Example 2 Except that 75.0 g of 4-vinylbenzyl glycidyl ether was substituted with 4-hydroxybutyl acrylate glycidyl ether (product of Nippon Kasei Co., Ltd.: 4HBAGE) 8 1 .0 g, the other system was implemented. In the same manner as in Example 1, a photosensitive resin (A2) solution of a pale yellow transparent viscous liquid was obtained. This solution was analyzed in the same manner as in Example 1 to give a viscosity of 330 mPa·s/25 °C, a weight average molecular weight of 4,920 in terms of styrene obtained by GPC, and a solid acid value of 54.8 mgKOH/g. Example 3 In a 1000 ml flask equipped with a stirrer and a cooling tube, biphenyltetracarboxylic dianhydride (product of Ube Industries, Ltd.: BPDA) was placed. 67.5 g, 9,9-φ bis [4- ( 2- Hydroxyethoxy)phenyl]indole (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF) 82.5 g, 4-dimethylaminopyridine 0.9 g, propylene glycol monomethyl ether acetate l〇〇g, stirred under a nitrogen stream It was heated in an oil bath at 155 ° C for 4 hours. Then, after cooling to 120 ° C, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo (Adekastab LA-7RD, manufactured by ADEKA) was added, 0.03 g, 2-hydroxyethyl The acrylate was 12.0 g, and stirring was continued at 120 ° C for 4 hours. Further, 42.0 g of 4-vinylbenzyl glycidyl ether was added, and the mixture was stirred at 120 ° C for 2 hours. Then, cool to room temperature. A propylene glycol mono-23-200949444 methyl ether acetate was added so as to have a nonvolatile content of 50% by weight to obtain a pale yellow transparent viscous photosensitive resin (A3) solution. This solution was analyzed in the same manner as in Example 1 to give a viscosity of 2,860 mPa·s/25 ° C, a styrene-equivalent weight average molecular weight of 6,610 obtained by GPC, and a solid acid value of 65.2 mgKOH/g. Example 4 The same procedure as in Example 3 except that 4-vinylbenzyl glycidyl ether 42_0 g was substituted with 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) 45.0 g The reaction was carried out to obtain a photosensitive resin (A4) solution of a pale yellow transparent viscous liquid. This solution was analyzed in the same manner as in Example 1 to obtain a viscosity of 990 mPa·s/2 5 ° C, a weight average molecular weight of 6,000 in terms of GPC, and a solid molecular weight of 64.5 mgKOH/g. . Example 5 In a flask equipped with a stirrer and a cooling tube of 100 ml, a biphenyltetracarboxylic dianhydride (product of Ube Industries Co., Ltd.: BPDA) was placed in an amount of 75 g, and bisphenol A was added to ethylene oxide. (manufactured by Nippon Emulsifier Co., Ltd.: BA2 glycol) 75 g, 4-dimethylaminopyridine 0.9 g, propylene glycol monomethyl ether acetate l〇〇g, oil bath at 155 ° C while stirring under a nitrogen stream Heat in 4 hours. Then, after cooling to 120 ° C, 4-hydroxy-2,2,6,6-tetramethylhexahydroport was added to steep-1-oxo (Adekastab LA-7RD, manufactured by ADEKA) 0.03 g, 2-hydroxyl Ethyl acrylate 6.0 g was continuously stirred at 120 ° C for 4 hours. Further, 51 g of 4-vinylbenzyl glycidyl ether was added and stirred at 120 ° C -24-

200949444 Mix for 2 hours. Then, it was cooled to room temperature. A propylene glycol monomethyl ether acetate was added in such a manner that the nonvolatile content was in the form of a shoulder amount to obtain a light-sensitive photosensitive resin (A5) solution. After the solution was analyzed and carried out, the viscosity was 1 960 mPa·s / 25 ° C, and the obtained styrene-converted weight average molecular weight was 12,470, and the solid form was 69 mgKOH/g. Example 6 except that 4-vinylbenzene was used. Methyl glycidyl ether 51 g-substituted butyl acrylate glycidyl ether (4HBAGE, Nippon Kasei Co., Ltd.), except for 54 g, was reacted in the same manner as in Example 5 to obtain a photosensitive property of a pale yellow transparent viscous liquid. Resin solution. This solution was analyzed in the same manner as in Example 1 to obtain a molecular weight of 14,200 mKOH/g in terms of styrene in terms of styrene in terms of styrene in terms of 1,4-100 mPa·s/2 5 °C. & 50 weight yellow transparent example 1 with GPC acid value into 4-hydroxy products: piece into (A6) for viscosity average

Comparative Example 1 Using a bisphenol fluorene-type epoxy resin having an epoxy group equivalent of 257 (manufactured by Si Chemical Co., Ltd.: BPFG), according to Synthesis Example 1 and Example 1 of Patent Document 3 (Japanese Patent Publication No. F325494), sensitization was obtained ( A7). It takes more than 20 hours for the synthesis system, and the productivity is significantly lower than that of the present examples 1 to 4. Comparative Example 2 Osaka Wasinping 9-seal Resin Mingzhi-25- 200949444 A bisphenol oxime type epoxy resin (BPFG manufactured by Osaka Gas Chemical Co., Ltd.) having an epoxy equivalent of 25 7 was used, according to Patent Document 3 (Special Kaiping) In Synthesis Example i and Example 2 of 9-3, No. 494, a photosensitive resin (A8) was obtained. It takes more than 2 hours for the synthesis system to be significantly lower than that of the inventive examples 1 to 4 of the present invention. Comparative Example 3 The same conditions as in Example 3 were carried out except that 42.0 g of 4-vinylbenzyl glycidyl ether was substituted with glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.: GMA) of 1 8.0 g. The reaction was carried out to obtain a photosensitive resin (A9) solution of a pale yellow transparent viscous liquid. This solution was analyzed in the same manner as in Example 1 to give a viscosity of 8,100 mPa·s/25 ° C, a weight average molecular weight of 5,200 in terms of styrene in terms of GPC, and a solid acid value of 86.5 mgKOH/g. Comparative Example 4 The same procedure as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was substituted with glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.: GM A) 21.1 g The reaction was carried out to obtain a photosensitive resin (A 10 ) solution of a pale yellow transparent viscous liquid. This solution was analyzed in the same manner as in Example 1 to give a viscosity of 7,800 mPa·s/25 ° C, a weight average molecular weight of 6,000 in terms of GPC, and a solid molecular weight of 75.6 mgKOH/g. -26- 200949444 Test Example 1 The photosensitive resins of Examples 1 to 6 and Comparative Examples 1 and 2 were measured for the polystyrene-equivalent weight average molecular weight obtained by GPC after storage for one month after production and at room temperature. Its rate of change. The results are shown in Table 1. [Table 1] Polystyrene-converted polystyrene-equivalent average molecular weight change after 1 month after manufacture Example 1 5330 5280 99.1% Example 2 4920 4720 95.9% Example 3 6610 6740 102.0% Example 4 6200 6390 103.1% Example 5 12470 12657 101.5% Example 6 14200 14271 100.5% Comparative Example 1 5840 7180 122.9% Comparative Example 2 6340 7930 125.1% The photosensitive resin of Examples 1 to 6 showed almost no change, but the ratio 0 The photosensitive resin of the examples 1 to 2 showed an increase in molecular weight of about 25%, which was poor in storage stability. Example 7 Using the photosensitive resin A1 obtained in Example 1, a photosensitive resin composition shown in the following Table 2 was prepared. This photosensitive resin composition was applied to a dry glass film having a thickness of 3 mm by a spin coater on a 1.1-thick sodium glass substrate, and dried on a hot plate at 1 ° C for 90 seconds, and then cooled to room temperature. Then, with an ultra-high pressure mercury lamp exposure machine, the ultraviolet light illumination is 15 mW/cm2 (3 65 mm), -27-200949444, and the integrated light amount is 20 mJ/cm2, and UGRA-OFFSET-TEST KAIL 1982 is used as a mask for soft contact exposure. 'The image was immersed in 1% sodium carbonate water at 25 °C for 90 seconds to form a pattern, and the sensitivity was evaluated by the order of the remaining steps, and the resolution was evaluated by a fine line. The results are shown in Table 2. Example 8 to 10 and Comparative Examples 5 to 8 A photosensitive resin composition was prepared in the same manner as in Example 7 except that the photosensitive resin A1 was replaced by the photosensitive resin A2 to A10, and the sensitivity and resolution were evaluated. . The results are shown in Table 2.

-28- 200949444

_[Table 2]_ EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES Comparative Example Comparative Example Comparative Example Comparative Example___7 8 9 10 Photosensitive Resin A1 2.00 Photosensitive Resin A2 Photosensitive Resin A3 Photosensitive Resin A4 Photosensitive Resin A5 Photosensitive resin A6 Photosensitive resin A7 Photosensitive resin A8 Photosensitive resin A9 Photosensitive resin A10 π_ 12 5 6 7 8 2.00 2.00 2.00 2.00 2.00 2.00 2.00

Irgacure OXE-Ol^1 0.05 0.05 0.05 0.05 DPHA*2 0.50 0.50 0.50 0.50 PGMEA*3 2.62 2.62 2.62 2.62 Step sensitivity 4 6 5 8 Resolution [μ m ] Line 4 6 4 4 2.00 2.00 0.05 0.05 0.05 0.05 0.05 0.50 0.50 0.50 0.50 0.50 0.50 2.62 2.62 2.62 2.62 2.62 2.62 5 7 3 3 2 2 6 6 6 6 6 6

※丄1,2-octanedione, 1-[4-(phenylsulfanyl)-, 2_(o-benzylidene fluorenyl)], bisba pentaerythritol hexaacrylate manufactured by Ciba Specialty Chemical Co., Ltd.: Nippon Chemical *3 propylene glycol monomethyl ether acetate was used as the photosensitive composition of the photosensitive resin of Comparative Examples 1 to 4, and the photosensitive composition of the photosensitive resin of Example 1 had a high sensitivity and showed good Photoresist characteristics. [Industrial Applicability] The photosensitive resin of the present invention is excellent in chemical resistance and heat resistance, and has high productivity and excellent storage stability in the case of -29-200949444, and the photosensitive resin composition is highly sensitive. And it has good patterning property, so it can be suitably used for the use of a photoresist. -30-

Claims (1)

200949444 VII. Patent application range: 1. A photosensitive resin characterized by a polymer compound obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (2). Addition of a carboxylic acid-reactive compound having an ethylenically unsaturated group, and [Chemical 1] (wherein Y represents -CO-, -S02-, -C(CF3) 2- '-Si (CH3) 2-, -CH2-, _C (CH3) 2-, _〇_, cyclohexyl, 9, 9-fluorenyl or direct bonding, R1, R2 independently represent a hydrogen atom or a methyl group, and n, m independently represent the number of 0 to 4) (2) (wherein X represents a tetravalent carboxylic acid residue). 2. The photosensitive resin according to claim 1, wherein the ratio of the compound represented by the formula (2) to the compound 10 represented by the formula (1) is 1 10 to 200 mol. The scope of the share. 3. The photosensitive resin according to claim 1 or 2, wherein the carboxylic acid-reactive compound having an ethylenically unsaturated group is represented by the following formula (3), -31 - 200949444 (3) The photosensitive resin according to any one of claims 1 to 3, wherein the carboxylic acid-reactive compound having an ethylenically unsaturated group is represented by the following formula (4), [Chem. 4] R3 (wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a group which is not represented by the following formula (5)) C2h4o C3h6o C4h8 (5) (In the formula, Γ, s, and t each independently represent an integer of 〇~9, but Γ, s, and t are not 〇). The photosensitive resin obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (2), wherein the photosensitive resin of the compound of the formula (1) is reacted with the compound of the formula (2). Further compounded with a compound represented by the following formula (6) or water, [Chem. 6] -32- 200949444 (wherein R5 represents a hydrogen atom or a methyl group, and R6 represents a group represented by a formula of t A) ~^-〇2Η4〇 c3h6o C4h8o (7) (In the formula, l, p, and q respectively represent integers from 0 to 9, but lxf and q are not 0 at the same time).感光 6 The photosensitive resin of any one of claims 1 to 5 wherein Y in the formula (1) is 9,9-fluorenyl. 7. The photosensitive resin according to any one of claims 1 to 6, wherein the acid value is 30 to 150 mgKOH/g. A photosensitive resin composition comprising the photosensitive resin according to any one of items 1 to 7 of the invention, and a photopolymerization initiator and/or a photosensitizer. 9. The photosensitive resin composition of claim 8, wherein φ further contains a polymerizable monomer having one or more unsaturated groups in the molecule. -33- 200949444 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: none -3- 200949444 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none