JP5142161B2 - Photosensitive resin and photosensitive resin composition using the same - Google Patents

Description

  The present invention relates to a photosensitive resin and a photosensitive resin composition using the same, and more specifically, can be easily produced at low cost, has high sensitivity, and is particularly used for negative photolithography. In particular, the present invention relates to a photosensitive resin and a photosensitive resin composition that exhibit good patterning properties.

  High molecular compounds with radically polymerizable unsaturated bond structure (vinyl group) in the molecule are used in various fields as photosensitive compositions and thermosetting compositions by utilizing the crosslinking reaction by polymerization of vinyl groups. Yes. Among them, photosensitive resins having a bisphenol-type aromatic polyester structure in the main chain are excellent in heat resistance and chemical resistance, so many have been proposed so far, such as liquid crystal color filters, black matrices, It is applied to a photoresist such as a solder resist (Patent Documents 1 to 3).

  However, all of the photosensitive resins described in these documents are those in which acrylic acid is added to an epoxy compound and then polyesterified with tetrabasic acid dianhydride, and the manufacturing process is complicated and requires a long time. Therefore, the manufacturing cost was high. Further, although the physical properties required for photoresists differ depending on the application, these photosensitive resins have a drawback that they cannot be applied to a wide range of applications because it is difficult to adjust the crosslinking density and the acid value. Furthermore, it cannot be said that resist characteristics such as sensitivity are sufficient when used in a photoresist.

JP 2006-276421 A JP 2006-003860 A JP-A-9-325494

  Accordingly, there is a need to provide a photosensitive resin that can be easily produced at low cost and can be applied to a wide range of applications because of easy adjustment of the crosslinking density and acid value, and is excellent in sensitivity. An object of the present invention is to provide such a photosensitive resin and a photosensitive resin composition using the same.

  In view of such circumstances, the present inventors have conducted extensive research to solve the above problems, and as a result, the polymer compound obtained by reacting a specific bisphenol with an acid dianhydride has an ethylenically unsaturated group. A photosensitive resin obtained by adding a carboxylic acid-reactive compound having a group can be easily produced at low cost, and it is easy to adjust a crosslinking density and an acid value, and has high sensitivity and excellent patternability. As a result, the present invention has been completed.

（式中、Ｙは−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、シクロヘキシル基、９，９−フルオレニル基又は直結合を示し、Ｒ^１、Ｒ^２は独立に水素原子又はメチル基を示し、ｎ、ｍは独立に０〜４の数を示す。）

（式中、Ｘは４価のカルボン酸残基を示す。）That is, the present invention provides a carboxylic acid reactivity having an ethylenically unsaturated group to a polymer compound obtained by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2). It is a photosensitive resin obtained by adding a compound.

(Wherein, Y is _{-CO -, - SO 2 -,} - C (CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O- A cyclohexyl group, a 9,9-fluorenyl group or a direct bond, R ¹ and R ² independently represent a hydrogen atom or a methyl group, and n and m independently represent a number of 0 to 4.)

(In the formula, X represents a tetravalent carboxylic acid residue.)

  Moreover, this invention contains the said photosensitive resin, a photoinitiator, and / or a photosensitizer, The photosensitive resin composition characterized by the above-mentioned.

  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, has excellent productivity, and is easy to adjust the crosslinking density and acid value. Applicable to a wide range of applications. Moreover, the photosensitive resin composition using this photosensitive resin has high sensitivity and good patternability.

The polymer compound constituting the photosensitive resin of the present invention is obtained by reacting a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

In the formula, Y represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, A cyclohexyl group, a 9,9-fluorenyl group or a direct bond; R ¹ and R ² independently represent a hydrogen atom or a methyl group; and n and m independently represent a number of 0 to 4.

  Specific examples of the compound represented by the general formula (1) (hereinafter sometimes referred to as “compound (1)”) include bisphenol A, ethoxylated bisphenol A, bisphenol F, ethoxylated bisphenol F, 4, 4'-biphenol, 3,3'-biphenol, ethoxylated 4,4'-biphenol, ethoxylated 3,3'-biphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, ethoxylated 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybenzophenone, ethoxylated 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfone, ethoxylated bis (4-hydroxyphenyl) sulfone, 2,2- Bis (4-hydroxyphenyl) hexafluoropropane, ethoxy 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, ethoxylated bis (4-hydroxyphenyl) dimethylsilane, 4,4′-dihydroxydiphenyl ether, ethoxylated 4,4 '-Dihydroxydiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-hydroxyethoxy) Phenyl] fluorene and the like can be exemplified, and one or more of these can be used. Among these, those in which Y in the general formula (1) is a 9,9-fluorenyl group are preferable. Specifically, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] Fluorene is preferred, and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is most preferred.

  Of the compounds (1), the method for synthesizing the ethoxylated compound is not particularly limited. Even if the compound is synthesized by adding ethylene oxide to a phenolic compound, phenoxyethanol is added to the corresponding ketone or carboxylic acid by Friedel. -Although it may be added by a Crafts reaction, a method of adding phenoxyethanol is preferred because there is no distribution in the chain length of ethylene glycol and the physical properties can be easily designed.

（式中、Ｘは４価のカルボン酸残基を示す。）As the compound to be reacted with the compound (1), a compound represented by the following general formula (2) (hereinafter sometimes referred to as “compound (2)”) is used.

(In the formula, X represents a tetravalent carboxylic acid residue.)

  Compound (2) is an acid dianhydride, specifically, butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclohexane Pentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, cycloheptanetetracarboxylic dianhydride, norbornanetetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyl Tetracarboxylic 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- Trahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,4, 9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and the like can be exemplified, and one or more of these are used.

  A polymer compound constituting the photosensitive resin of the present invention is obtained by subjecting the above compound (1) to an addition reaction with the compound (2). In this addition reaction, the ratio of compound (2) to 100 mol parts of compound (1) is preferably in the range of 110 to 200 mol parts, more preferably 120 to 160 mol parts. When the amount is less than 110 parts by mole, the addition amount of the carboxylic acid-reactive compound having an ethylenically unsaturated group that contributes to the photosensitive performance cannot be increased, and sufficient photosensitive performance may not be obtained. On the other hand, when the amount exceeds 200 parts by mole, synthesis is difficult because the solubility of the raw materials is low, and the molecular weight necessary to form a coating film may not be obtained.

  A catalyst may be used in the addition reaction of the compound (1) and the compound (2). The catalyst to be used is not particularly limited as long as it promotes the reaction. Examples thereof include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N , N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, , 5-diazabicyclo [4,3,0] nonene-5, etc., quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, Fins, triphenylphosphine and the like and mixtures thereof. Moreover, there is no restriction | limiting in particular also in the quantity of the catalyst to be used, However, The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of compounds (1). If the amount of the catalyst is more than 2.0 parts by mass, the electrical characteristics and storage stability of the photosensitive resin may be adversely affected.

  Further, in the addition reaction, a solvent may be used for the purpose of dissolving the reaction raw materials and reducing the viscosity. The type of solvent is not particularly limited as long as it does not inhibit the reaction. Examples include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. Glycol ether acetates such as, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol ethers such as propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ete Propylene glycol ether acetates such as acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, dimethyl Examples include sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  Although there is no restriction | limiting in particular also in the quantity of the solvent to be used, The range of 25-150 mass parts is preferable with respect to a total of 100 mass parts of a compound (1) and a compound (2). If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.

  A solvent or a catalyst is added to the compound (1) and the compound (2) as necessary to cause an addition reaction. In the reaction, it is preferable to heat, the raw material is dissolved by the heating, and the reaction rate is also accelerated. Although heating temperature can be suitably set according to the kind of compound (1) and compound (2) and the apparatus to be used, the range of 60-220 degreeC is preferable in general. More preferably, it is the range of 90-160 degreeC. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, when the reaction temperature is higher than 220 ° C., side reactions such as coloring may occur, or the reaction rate may decrease due to an equilibrium in which the acid anhydride is closed.

  The photosensitive resin of this invention is obtained by making the carboxylic acid reactive compound which has an ethylenically unsaturated group react with the high molecular compound obtained as mentioned above. The carboxylic acid-reactive compound having an ethylenically unsaturated group (hereinafter sometimes simply referred to as “carboxylic acid-reactive compound”) has an ethylenically unsaturated group and easily reacts with carboxylic acid. If there is, it can be used without particular limitation, and specific examples include an epoxy compound having an ethylenically unsaturated group, an isocyanate compound, a vinyl ether compound, and a methylol compound.

  Specific examples of the epoxy compound include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, and a compound represented by the following general formula (4). .

（式中、Ｒ^３は水素原子又はメチル基を示し、Ｒ^４は下記一般式（５）で表される基を示す）

（式中、ｒ、ｓ、ｔはそれぞれ独立に０〜９の整数を示す。但し、ｒ、ｓ、ｔが同時に０となることはない。）

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a group represented by the following general formula (5))

(In the formula, r, s, and t each independently represent an integer of 0 to 9. However, r, s, and t are not 0 simultaneously.)

  Examples of the compound represented by the general formula (4) include 4-hydroxybutyl (meth) acrylate glycidyl ether, polyethylene glycol-polypropylene glycol (meth) acrylate glycidyl ether, and the like.

  Specific examples of isocyanate compounds include 2- (meth) acryloyloxyethyl isocyanate, and specific examples of vinyl ether compounds include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate as a methylol compound. N-methylol (meth) acrylamide etc. are mentioned.

Among these, an epoxy compound is preferable, and vinylbenzyl glycidyl ether and 4-hydroxybutyl (meth) acrylate glycidyl ether are particularly preferable. Vinyl benzyl glycidyl ether is a compound represented by the following general formula (3), and can improve heat resistance and chemical resistance.

  On the other hand, 4-hydroxybutyl (meth) acrylate glycidyl ether is preferably used because of its high sensitivity.

  Such a carboxylic acid reactive compound is subjected to an addition reaction with the polymer compound. Although the ratio of the carboxylic acid reactive compound in the photosensitive resin of the present invention varies depending on the use, it cannot be said unconditionally, but when applied to an alkali developable use, the acid value of the resin solid content is 30 to 150 mgKOH. It is preferable to adjust so that it exists in the range of / g. If the acid value is lower than 30 KOH / g, the development speed may be reduced and a required pattern may not be obtained. On the other hand, when the acid value is higher than 150 mgKOH / g, the pattern is likely to be peeled off due to excessive development, and the electrical characteristics and the like may be deteriorated. In addition, in this specification, the acid value of resin solid content is a measured value based on JIS-K0070.

  In the reaction between the polymer compound and the carboxylic acid reactive compound, a catalyst may be used for the purpose of promoting the reaction. The type of catalyst varies depending on the type of the carboxylic acid reactive compound, and thus cannot be generally stated. Examples include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, and N-ethylmorpholine. , Triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0]- Quaternary amines such as 7-undecene, 1,5-diazabicyclo [4,3,0] nonene-5, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, etc. Ammoniu Compounds, tributylphosphine, triphenylphosphine and the like and mixtures thereof.

  Moreover, there is no restriction | limiting in particular also in the quantity of the catalyst to be used, However, The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of compounds (1). If the amount of the catalyst is too large, the electrical properties and storage stability of the photosensitive resin may be adversely affected.

  Further, in reacting the carboxylic acid reactive compound, it is preferable to add a polymerization inhibitor. The type of the polymerization inhibitor is not particularly limited as long as it suppresses the reaction of unsaturated bond. Examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, N-methyl-N-nitroso. Aniline or N-nitrosophenylhydroxylamine / ammonium salt (Wako Pure Chemical Industries, Ltd .: Q-1300), N-nitrosophenylhydroxylamine / aluminum salt (Wako Pure Chemical Industries, Ltd .: Q-1301), 2, Examples include 2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. In particular, N-nitrosophenylhydroxylamine aluminum salt and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl are preferable. The amount of the polymerization inhibitor varies depending on the type and reaction conditions, and cannot be generally stated, but is preferably in the range of 5 to 2000 ppm with respect to the entire photosensitive resin. If it is less than this range, unsaturated bonds may react during production to cause gelation, and if it is more than this range, the sensitivity may decrease, which is not preferable.

  When adding a carboxylic acid reactive compound, it is preferable to heat for the purpose of improving the reaction rate. Although heating temperature can be suitably set with the kind and apparatus of a carboxylic acid reactive compound, the range of about 60-150 degreeC is preferable in general. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, if the reaction temperature is higher than 150 ° C., side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.

（式中、Ｒ^５は水素原子またはメチル基を示し、Ｒ^６は下記一般式（７）で表される基を示す。）

（式中、ｌ、ｐ、ｑはそれぞれ独立に０〜９の整数を示す。但し、ｌ、ｐ、ｑが同時に０となることはない。）The polymer compound obtained by reacting the compound (1) with the compound (2) has an excess of compound (2) with respect to compound (1) when the mixing ratio is as described above. It has a structure of things. Here, when an epoxy compound having an ethylenically unsaturated group is applied as the carboxylic acid reactive compound, the acid anhydride may react with the —OH group generated by the opening of the epoxy ring, resulting in an increase in molecular weight. In order to suppress an increase in molecular weight due to this reaction, it is preferable to react a compound having a hydroxyl group represented by the following general formula (6) or water with an acid anhydride structure site at the polymer end.

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a group represented by the following general formula (7).)

(In the formula, l, p and q each independently represent an integer of 0 to 9. However, l, p and q are not 0 simultaneously.)

  This reaction may be performed prior to or simultaneously with the addition of the epoxy compound having an ethylenically unsaturated group, but considering the reproducibility of the reaction, the reaction is performed prior to the reaction of the epoxy compound having an ethylenically unsaturated group. Is more preferable.

  Specific examples of the compound represented by the general formula (6) (hereinafter sometimes referred to as “compound (6)”) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples include 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, etc. Among these, crosslinking reactivity and cost From the above, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferably used.

  A catalyst may be used in reacting the compound (6) or water. The kind of the catalyst is the same as that which can be used at the time of the reaction of the compound (1) and the compound (2). The catalyst used in this reaction may be used as it is, or the same one may be added or another Different types of catalysts may be added separately. The reaction temperature is preferably in the range of 60 to 150 ° C. If the reaction temperature is too low, it may take time to complete the reaction. If the reaction temperature is too high, side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.

  The photosensitive resin prepared as described above can be taken out as a solid by spray drying, film drying, dropping into a poor solvent, reprecipitation, etc. for the purpose of purification, storage, solvent change and the like.

  The molecular weight of the photosensitive resin of the present invention is not particularly limited, but is preferably 1,500 to 100,000, more preferably 2,000 to 20,000. Within this range, a good balance between coating film strength and developability is preferable. In the present specification, the molecular weight of the photosensitive resin is a weight average molecular weight in terms of styrene by GPC under the conditions described in the examples.

  The photosensitive resin composition of this invention contains the said photosensitive resin and a photoinitiator and / or a photosensitizer as an essential component. The photopolymerization initiator and / or photosensitizer may be mixed in a state dissolved or dispersed in a solvent, or chemically bonded to the photosensitive resin.

  The photopolymerization initiator and / or photosensitizer used in the present invention is not particularly limited, and examples thereof include benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, and bis-N. Benzophenones such as N, diethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone and isopropoxychlorothioxanthone, ethyl anthraquinone, benzanthraquinone Anthraquinones such as aminoanthraquinone, chloroanthraquinone, anthraquinone-2-sulfonate, anthraquinone-2,6-disulfonate, acetophenones, benzo Benzoin ethers such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, 2,4,6-trihalomethyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole Dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole 2,4,5-triarylimidazole dimers such as dimer, benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], phenanthrenequinone, 9,10-phenanthrenequinone, benzoins such as methylbenzoin, ethylbenzoin, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Heptane, etc., acridine derivatives, include bisacylphosphine oxide, can be used alone or in combination of two or more thereof.

  An accelerator may be further added to the photosensitive resin of the present invention. Examples of the accelerator include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine 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 sometimes simply referred to as “polymerizable monomer”) can be used. , Chemical resistance, heat resistance and mechanical strength can be improved. Moreover, it is also possible to add a polymerizable monomer for the purpose of adjusting flow characteristics. As the polymerizable monomer, any monomer having at least one unsaturated bond in the molecule can be used without particular limitation, and an appropriate monomer may be selected depending on the intended use and purpose. For example, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, Trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups), dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A polyoxyethylene di (meth) acrylate, bisphenol A dioxyethylene Di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, polyvalent carboxylic acid (such as phthalic anhydride), a compound having a hydroxyl group and an ethylenically unsaturated group ( β-hydroxyethyl (meth) acrylate, etc.), (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, etc. (Meth) acrylic acid alkyl ester, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycol Of epoxy compounds such as cidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether, glycerin triglycidyl ether (Meth) acrylic acid adducts, unsaturated organic acids such as maleic acid and their anhydrides, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylmethacrylamide, N- Ethyl methacrylamide, N-isopropyl methacrylamide, N-methylol methacrylamide, N, N-dimethyl acryl , Acrylamides such as N, N-diethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, styrenes such as styrene and hydroxystyrene, N-vinylpyrrolidone, N-vinylformamide, N- Examples thereof include vinylacetamide and N-vinylimidazole, and one or more of these can be used.

  A colorant can also be added to the photosensitive resin composition of the present invention for the purposes of design, visibility, and prevention of photoresist halation. The kind of colorant to be added can be appropriately selected depending on the purpose of coloring. For example, phthalocyanine dyes, anthraquinone dyes, azo dyes, indigo dyes, coumarin dyes, triphenylmethane dyes, phthalocyanine pigments Anthraquinone pigments, azo pigments, quinacridone pigments, coumarin pigments, triphenylmethane pigments and the like can be exemplified, and one or more of these can be used.

  The photosensitive resin composition of this invention can be made into the form of a solution or a paste, For that purpose, it is also possible to contain a solvent. The type of solvent used is not particularly limited, but examples include water, ethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol. Glycol ethers such as dimethyl ether, glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol, propylene glycol monomethyl ether Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether and other propylene glycol ethers, propylene glycol monomethyl ether acetate , Propylene glycol ether acetates such as propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl lactate, lactate ester Lactate esters such as Le, ethyl acetate, acetic acid esters such as butyl acetate, dimethyl sulfoxide, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  In the photosensitive resin composition of the present invention, conventionally known components such as a polymerization inhibitor, a plasticizer, an antifoaming agent, and a coupling agent can be further blended as necessary.

  The photosensitive resin composition of this invention can be obtained by mixing the said essential component and a solvent and other arbitrary components as needed according to a conventional method.

  The photosensitive resin composition of the present invention obtained as described above can be used for photoresist applications such as liquid crystal color filters, black matrices, and solder resists. When used as a photoresist, the photosensitive resin composition of the present invention is applied on a substrate as a solution or a paste. The coating method is not particularly limited, and screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, slit coating, and the like are applied. The applied solution or paste is exposed with UV or electron beam through a predetermined mask. When apply | coating using a solvent, you may pass through a drying process. A pattern can be formed by developing the exposed coating film wet. The developing method can be any of a spray method, a paddle method, an immersion method, and the like, but a spray method with few residues is preferable. Ultrasonic waves or the like can be irradiated as necessary. As the developer, weak alkaline water is preferably used. For the purpose of assisting developability, an organic solvent, a surfactant, an antifoaming agent, etc. can be added.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these.

Example 1
In a 1000 ml flask equipped with a stirrer and a condenser, 67.5 g of pyromellitic dianhydride (Daicel product: PMDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) 82.5 g (manufactured by BPEF) and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours while stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.9 g of 4-dimethylaminopyridine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: ADK STAB LA-7RD) 03 g and 30.0 g of 2-hydroxyethyl acrylate were added, and stirring was continued at 120 ° C. for 4 hours. Furthermore, 75.0 g of 4-vinylbenzyl glycidyl ether was added and stirred at 120 ° C. for 2 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A1) solution.

  The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 420 mPa · s / 25 ° C., styrene-converted weight average molecular weight by GPC was 5,330, and solid content acid value was 52. 0.0 mg KOH / g. In addition, Toki Sangyo Co., Ltd. BM type | mold viscosity meter was used for the viscosity measurement. Further, GPC was measured using TSKgel G7000HXL, TSKgel GMHXL 2 and TSKgel G2500HXL manufactured by Tosoh Corporation at a THF eluent of 40 ° C. and a flow rate of 0.5 ml / min. The acid value was measured according to the neutralization titration method described in JIS-K0070.

Example 2
Photosensitivity of a light yellow transparent viscous liquid in the same manner as in Example 1 except that 75.0 g of 4-vinylbenzyl glycidyl ether was replaced with 81.0 g of 4-hydroxybutyl acrylate glycidyl ether (product of Nippon Kasei Co., Ltd .: 4HBAGE). Resin (A2) solution was obtained. When this solution was analyzed in the same manner as in Example 1, the viscosity was 330 mPa · s / 25 ° C., the weight average molecular weight was 4,920 in terms of styrene by GPC, and the acid value was 54.8 mgKOH / g.

Example 3
In a 1000 ml flask equipped with a stirrer and a condenser tube, 67.5 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka) Gas Chemical Company: BPEF) 82.5 g, 4-dimethylaminopyridine 0.9 g, and propylene glycol monomethyl ether acetate 100 g were added and heated in a 155 ° C. oil bath for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.03 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (product of ADEKA: Adeka Stab LA-7RD), 2-hydroxyethyl acrylate 12. 0 g was added and stirring was continued at 120 ° C. for 4 hours. Further, 42.0 g of 4-vinylbenzyl glycidyl ether was added and stirred at 120 ° C. for 2 hours. Next, it was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light brown transparent viscous photosensitive resin (A3) solution. When this solution was analyzed in the same manner as in Example 1, it was found that the viscosity was 2860 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,610, and the solid content acid value was 65.2 mgKOH / g.

Example 4
The reaction was conducted under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was replaced with 45.0 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). When this solution obtained as a liquid photosensitive resin (A4) solution was analyzed in the same manner as in Example 1, the viscosity was 990 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,200, and the solid content acid value was 64. 0.5 mg KOH / g.

Example 5
In a 1000 ml flask equipped with a stirrer and a condenser, 75 g of biphenyltetracarboxylic dianhydride (Ube Industries product: BPDA), 75 g of ethylene oxide-added bisphenol A (Nippon Emulsifier Co., Ltd .: BA2 glycol), 4-dimethylaminopyridine 0 0.9 g and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.03 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: ADK STAB LA-7RD) and 6 g of 2-hydroxyethyl acrylate were added. In addition, stirring was continued at 120 ° C. for 4 hours. Further, 51 g of 4-vinylbenzyl glycidyl ether was added and stirred at 120 ° C. for 2 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A5) solution. When this solution was analyzed in the same manner as in Example 1, the viscosity was 1960 mPa · s / 25 ° C., the weight-average molecular weight was 12,470 in terms of styrene by GPC, and the solid content acid value was 69 mgKOH / g.

Example 6
The reaction was carried out under the same conditions as in Example 5 except that 51 g of 4-vinylbenzyl glycidyl ether was replaced with 54 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). A photosensitive resin (A6) solution was obtained. This solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 1,430 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 14,200, and the solid content acid value was 68.5 mgKOH / g.

Comparative Example 1
Using a bisphenolfluorene type epoxy resin having an epoxy equivalent of 257 (Osaka Gas Chemical Co., Ltd. product: BPFG), a photosensitive resin (A7) is obtained according to Synthesis Example 1 and Example 1 of Patent Document 3 (Japanese Patent Laid-Open No. 9-325494). It was. The synthesis took 20 hours or more, and the productivity was remarkably low as compared with Examples 1 to 4 of the present invention.

Comparative Example 2
Using a bisphenolfluorene type epoxy resin having an epoxy equivalent of 257 (Osaka Gas Chemical Co., Ltd. product: BPFG), the photosensitive resin (A8) was prepared according to Synthesis Example 1 and Example 2 described in Patent Document 3 (Japanese Patent Laid-Open No. 9-325494). Obtained. The synthesis took 21 hours or more, and the productivity was remarkably low as compared with Examples 1 to 4 of the present invention.

Comparative Example 3
The reaction was carried out under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzylglycidyl ether was replaced with 18.0 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA). (A9) A solution was obtained. The solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 8,100 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 5,200, and the solid content acid value was 86.5 mgKOH / g.

Comparative Example 4
The reaction was conducted under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was replaced with 21.1 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA), and a light yellow transparent viscous liquid photosensitive resin. (A10) A solution was obtained. This solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 7,800 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,500, and the solid content acid value was 75.6 mgKOH / g.

Test example 1
About the photosensitive resin of Examples 1-6 and Comparative Examples 1-2, the polystyrene conversion weight average molecular weight by GPC immediately after manufacture and 1 month after room temperature preservation | save was measured, and the change rate was investigated. The results are shown in Table 1.

  The photosensitive resins of Examples 1 to 6 showed almost no change, but the photosensitive resins of Comparative Examples 1 and 2 showed an increase in molecular weight of about 25% and were inferior in storage stability.

Example 7
Using the photosensitive resin A1 obtained in Example 1, a photosensitive resin composition was prepared with the formulation shown in Table 2 below. This photosensitive resin composition was applied to a 1.1 mm thick soda lime glass substrate with a spin coater to a dry film thickness of 3 μm, dried on a hot plate at 100 ° C. for 90 seconds, and then cooled to room temperature. Subsequently, after performing soft contact exposure using an UGRA-OFFSET-TEST KAIL 1982 as a mask at an ultraviolet illuminance of 15 mW / cm ² (365 nm) and an integrated light quantity of 20 mJ / cm ² with an ultra-high pressure mercury lamp exposure machine, A pattern was formed by immersing in 90% aqueous sodium carbonate for 90 seconds, and the sensitivity was evaluated by the number of remaining steps, and the resolution was evaluated by a microline. The results are also shown in Table 2.

Examples 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 with the photosensitive resins A2 to A10, and the sensitivity and resolution were evaluated. The results are also shown in Table 2.

  Compared with the photosensitive composition using the photosensitive resin of Comparative Examples 1-4, the photosensitive composition using the photosensitive resin of Examples 1-6 showed high sensitivity and the favorable resist characteristic.

  The photosensitive resin of the present invention is excellent in chemical resistance and heat resistance, has high productivity and excellent storage stability, and the photosensitive resin composition using the photosensitive resin has high sensitivity and good patternability. Therefore, it is suitably used for photoresist applications.

Claims (7)

A carboxylic acid-reactive compound having an ethylenically unsaturated group is added to a polymer compound obtained by reacting a compound represented by the following general formula (1) and a compound represented by the following general formula (2). A photosensitive resin obtained ,
A photosensitive resin in which the carboxylic acid-reactive compound having an ethylenically unsaturated group is represented by the following general formula (3) or the following general formula (4) .

(Wherein, Y is _{-CO -, - SO 2 -,} - C (CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O- A cyclohexyl group, a 9,9-fluorenyl group or a direct bond, R ¹ and R ² independently represent a hydrogen atom or a methyl group, and n and m independently represent a number of 0 to 4.)

(In the formula, X represents a tetravalent carboxylic acid residue.)

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a group represented by the following general formula (5))

(In the formula, r, s, and t each independently represent an integer of 0 to 9. However, r, s, and t are not 0 simultaneously.)   2. The photosensitive resin according to claim 1, wherein the ratio of the compound represented by the general formula (2) to 100 mol parts of the compound represented by the general formula (1) is in the range of 110 to 200 mol parts. In formula (1) compound and formula (2) compound polymer compound obtained by reacting a represented by represented by, by adding a compound or water represented by the following general formula (6), it further general formula (3) or general formula (4) with ethylene photosensitive resin according to claim 1 or 2 unsaturated groups by adding an acid reactive compound having a shall obtained represented.

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a group represented by the following general formula (7).)

(In the formula, l, p and q each independently represent an integer of 0 to 9. However, l, p and q are not 0 simultaneously.) Formula (1) Y in is 9,9-fluorenyl group claim 1 to a photosensitive resin according to any one of the paragraphs 3. The photosensitive resin according to any one of claims 1 to 4 , which has an acid value of 30 to 150 mgKOH / g. Photosensitive resin and a photopolymerization initiator and / or a photosensitive resin composition characterized by containing a photosensitizer according to any one of claims 1 to 5. Furthermore, the photosensitive resin composition of Claim 6 which contains the polymerizable monomer which has a 1 or more unsaturated group in a molecule | numerator.