KR20110013361A - Photosensitive resin and photosensitive resin composition comprising the same - Google Patents

Abstract

(식에서 Y는 -CO-, -ＳＯ₂-, -C(ＣＦ₃)₂-, -Ｓｉ(ＣＨ₃)₂-, -ＣＨ₂-, -C(ＣＨ₃)₂-, -O-, 시클로헥실기, 9,9-플루오렌일기 또는 직접결합을 나타내고, R¹, R²는 독립적으로 수소원자 또는 메틸기를 나타내고, n, m은 독립적으로 0∼4의 수를 나타낸다)
[식 2]

(식에서 X는 4가의 카르복시산 잔기를 나타낸다)It is an object of the present invention to provide a photosensitive resin which can be easily manufactured at low cost and can be easily adjusted to a crosslinking density and an acid value, which is applicable to a wide range of applications, and which has high sensitivity and excellent patterning property.
The photosensitive resin is a photosensitive resin obtained by adding a carboxylic acid reactive compound 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). .
[Equation 1]

Wherein Y is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, cyclo A hexyl group, a 9,9-fluorenyl group or a direct bond, R ¹ , R ² independently represent a hydrogen atom or a methyl group, n, m independently represent a number of 0 to 4)
[Formula 2]

(Where X represents a tetravalent carboxylic acid residue)

Description

Photosensitive resin and photosensitive resin composition using the same {PHOTOSENSITIVE RESIN AND PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a photosensitive resin and a photosensitive resin composition using the same. More particularly, the present invention can be easily manufactured at low cost and is particularly negative as a high sensitivity. The present invention relates to a photosensitive resin and a photosensitive resin composition exhibiting good patterning properties when used for negative photolithography.

Polymeric compounds having a radical polymerizable unsaturated bond structure (vinyl group) in a molecule are used in various fields as a photosensitive composition or a thermosetting composition by using a crosslinking reaction by polymerization of a vinyl group. It is used. Among them, photosensitive resins having a bisphenol-type aromatic polyester structure as the main chain, in particular, have been proposed until now because of their excellent heat resistance and chemical resistance, and thus, liquid crystal color filters. It is applied to photoresist, such as a black matrix and a solder resist (patent documents 1-3).

However, all of the photosensitive resins described in these documents are polyesterized with tetrabasic dianhydride after addition of acrylic acid to an epoxy compound, which makes the manufacturing process complicated and requires a long time. The manufacturing cost was high. Moreover, although the physical properties required by a photoresist differ also with a use, since these photosensitive resins are difficult to adjust a crosslinking density and an acid value, there existed a drawback that it cannot apply to a wide range of uses. Moreover, when used for a photoresist, it cannot be said that resist characteristics, such as a sensitivity, are enough.

Japanese Laid-Open Patent Publication No. 2006-276421 Japanese Patent Laid-Open No. 2006-003860 Japanese Patent Laid-Open No. 9-325494

Therefore, since it can be easily manufactured at low cost, and it is easy to adjust a crosslinking density and an acid value, it is applicable to a wide range of uses, and the provision of the photosensitive resin excellent in the sensitivity is calculated | required, This invention uses such a photosensitive resin and this Let it be a subject to provide the photosensitive resin composition.

In view of the above situation, the present inventors have intensively studied to solve the above problems, and as a result, a carboxylic acid-reactive compound having an ethylenically unsaturated group in a polymer compound obtained by reacting a specific bisphenol and an acid dianhydride The photosensitive resin obtained by adding a carboxylic acid antimicrobial compound can be easily manufactured at low cost, and it is easy to adjust the crosslinking density and acid value, and finds an excellent patterning property with high sensitivity to complete the present invention. Reached.

That is, this invention is the photosensitive resin obtained by adding the carboxylic acid reactive compound which has an ethylenically unsaturated group to the high molecular compound obtained by making the compound represented by following General formula (1) react with the compound represented by following General formula (2). .

[Equation 1]

Wherein Y is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, cyclo Hexyl group (cyclohexyl group), 9,9-fluorenyl group (9,9-fluorenyl group) or a direct bond, R ¹ , R ² independently represent a hydrogen atom or a methyl group (methyl group), n, m Independently represents a number from 0 to 4)

[Equation 2]

(Where X represents a tetravalent carboxylic acid residue)

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

Since the photosensitive resin of this invention is excellent in chemical resistance, heat resistance, high storage stability, can be manufactured easily at low cost, and is excellent in productivity, it is easy to adjust crosslinking density and acid value, and it is applicable to a wide range of uses. Moreover, the photosensitive resin composition using this photosensitive resin is highly sensitive, and is equipped with favorable patterning property.

The high molecular compound which comprises the photosensitive resin of this invention is obtained by making the compound represented by following General formula (1) and the compound represented by General formula (2) mentioned later react.

[Equation 1]

Wherein Y is -CO-, -S0 _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, cyclohex It represents a real group, a 9, 9- fluorenyl group, or a direct bond, R <^1> , R <^2> represents a hydrogen atom or a methyl group independently, n and m represent the number of 0-4 independently.

As a compound represented by the said General formula (1) (Hereinafter, it may be called "compound (1)"). Specifically, bisphenol A (bisphenol A), ethoxylated bisphenol A, bisphenol F, ethoxylated bisphenol F , 4,4'-biphenol (4,4'-biphenol), 3,3'-biphenol, ethoxylated 4,4'-biphenol, ethoxylated 3,3'-biphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane (1,1-bis (4-hydroxyphenyl) cyclohexane), ethoxylated 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybenzophenol (4,4'-dihydroxybenzophenone), ethoxylated 4,4'-dihydroxybenzophenol, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ) Sulfone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane (2,2-bis (4-hydroxyphenyl) hexafluoropropane), ethoxylated 2,2-bis (4-hydroxyphenyl) hexafluoro Propane, bis (4-hydroxyphenyl) dimethylsilane (bis (4-hydroxyphenyl) dimethylsila ne), ethoxylated bis (4-hydroxyphenyl) dimethylsilane, 4,4'- dihydroxy diphenyl ether, ethoxylated 4,4'- dihydroxy diphenyl ether (4,4-dihydroxy diphenyl ether) , 9,9-bis (4-hydroxyphenyl) fluorene (9,9-bis (4-hydroxyphenyl) fluorene), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (9,9 -bis (4-hydroxy-3-methylphenyl) fluorene), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene) and the like, and one kind or two or more kinds thereof can be used. Among these, in general formula (1), it is preferable that X is a 9, 9- fluorenyl group. Specifically, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-hydroxy Methoxy) phenyl] fluorene is preferred, with 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene being most preferred.

The synthesis method of the ethoxylated compound in the compound (1) is not particularly limited, and may be synthesized by adding ethylene oxide to a phenol compound, and corresponding ketones Or phenoxyethanol may be added to the carboxylic acids by a Friedel-Crafts reaction.However, a method of adding phenoxyethanol may be a chain length of ethylene glycol. It is preferable because the length can be made constant and the design of physical properties is easy.

As the compound to react with the compound (1), a compound represented by the following general formula (2) (hereinafter may be referred to as "compound (2)") is used.

[Equation 2]

(Where X represents a tetravalent carboxylic acid residue)

Compound (2) is an acid dianhydride, specifically, butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, Cyclobutanetetracarboxylic dianhydride, Cyclopentanetetracarboxylic dianhydride, Cyclohexanetetracarboxylic dianhydride, Cycloheptane tetracarboxylic dianhydride (cycloheptanintetrahydroanborate) (norbornanetetracarboxylic dianhydride), pyromellitic acid dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride (biphenyltetracarboxylic dianhydride) dianhydride), biphenylethertetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride ( 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 (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) diphthalic anhydride (4,4') -(hexafluoroisopropylidene) diphthalic anhydride), 3,4,9,10-perylenetetracarboxylic acid dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride), 3,3 ', 4,4'-diphenylsulfatetetracarboxylic acid Dianhydrides (3,3 ', 4,4'-diphenylsulphonetetracarboxylic dianhydride) It may be, their one or more kinds are used.

Compound (2) is added to and reacted with compound (1) to obtain a polymer compound constituting the photosensitive resin of the present invention. In this addition reaction, the ratio of the compound (2) to 100 mol parts of the compound (1) is preferably in the range of 110 to 200 mol parts, more preferably 120 to 160 mol parts. When it is less than 110 mol parts, the addition amount of the carboxylic acid reactive compound which has an ethylenically unsaturated group which contributes to photosensitive performance cannot be increased, and sufficient photosensitive performance may not be obtained. On the other hand, when it exceeds 200 mol part, since the solubility of a raw material is low, synthesis | combination is difficult and the molecular weight required for forming a coating film may not be obtained.

You may use a catalyst at the time of addition reaction of said compound (1) and compound (2). The catalyst to be used is not particularly limited as long as it promotes the reaction, but 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 (1,8-diazabicyclo [5,4,0] -7-undecene), 1,5-diazabicyclo [4,3,0 ] Amines such as 1,5-diazabicyclo [4,3,0] -nonene-5), tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl Quaternary ammonium compounds such as trimethyl benzyl ammonium chloride, tetramethyl ammonium hydroxyde, tributylphosphine, triphenylphosphine, etc. And mixtures thereof. Moreover, there is no restriction | limiting in particular also in the quantity of the catalyst to be used, The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of compounds (1). When the amount of the catalyst is too large than 2.0 parts by mass, it may adversely affect the electrical properties and storage stability of the photosensitive resin.

In addition, in addition reaction, you may use a solvent for the purpose of melt | dissolution of a reaction raw material, viscosity reduction, etc. The type of solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether. Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate (glycol ether acetates), dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether diethyl ether), Propylene glycol ethers such as propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol ether acetates, acetone, methyl, such as dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ester acetates such as ethyl acetate and butyl acetate , Dimethylsulfoxide, N-meth Blood can be given pyrrolidone (N-methylpyrrolidone), in dimethylformamide (dimethylformamide), dimethylacetamide (dimethylacetamide) and a mixture 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 mass parts, a viscosity may not fully reduce. On the other hand, when it exceeds 150 parts by mass, the concentration of the reactant may be too low, resulting in a decrease in the reaction rate.

The compound (1) and the compound (2) may be added and reacted with a solvent or a catalyst, if necessary, but heating is preferable during the reaction. The raw material is dissolved and the reaction rate is accelerated by heating. Although heating temperature can be set suitably according to the kind of compound (1) and compound (2), and the apparatus used, the range of 60-220 degreeC is generally preferable. More preferably, it is the range of 90-160 degree | times. If the reaction temperature is lower than 60 ° C, it may take a long time to complete the reaction. On the other hand, when reaction temperature is higher than 220 degreeC, side reactions, such as coloring, may generate | occur | produce, or reaction rate may fall by equilibrium which an acid anhydride ring-closes.

The photosensitive resin of this invention is obtained by making the high molecular compound obtained as mentioned above react with the carboxylic acid reactive compound provided with an ethylenically unsaturated group. The carboxylic acid reactive compound (hereinafter may be simply referred to as "carboxylic acid reactive compound") having an ethylenically unsaturated group can be used without particular limitation as long as it has an ethylenically unsaturated group and easily reacts with the carboxylic acid. An epoxy compound, an isocyanate compound, a vinyl ether compound, a methylol compound, etc. which have an ethylenically unsaturated group are mentioned.

Specific examples of the epoxy compound include glycidyl (meth) acrylate (glycidyl methacrylate), 3,4-epoxycyclohexylmethyl (meth) acrylate (3,4-epoxycyclohexylmethyl methacrylate), and vinyl benzyl glycidyl ether (vinyl benzyl). glycidyl ether), allyl glycidyl ether, the compound represented by following General formula (4), etc. are mentioned.

[Equation 4]

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

[Equation 5]

(In the formula, r, s, and t each independently represent an integer of 0 to 9. However, r, s, and t never become 0 at the same time.)

As a compound represented by the said General formula (4), 4-hydroxybutyl (meth) acrylate glycidyl ether (4-hydroxybutyl methacrylate glycidyl ether) and polyethyleneglycol polypropylene glycol (meth) acrylate glycidyl ether (polyethylene glycol-polypropylene glycol methacrylate glycidyl ether), etc. can be illustrated.

As a specific example of an isocyanate compound, 2- (meth) acryloyloxyethyl isocyanate etc. are mentioned, As a specific example of a vinyl ether compound, (meth) acrylic acid 2- (2-vinyloxyethoxy) Ethyl (2- (2-vinyloxyethoxy) ethyl (meth) acrylate) etc. are mentioned, As a methylol compound, N-methylol (meth) acrylamide (N-methylolmethacrylamide) etc. are mentioned.

Among these, an epoxy compound is preferable and vinyl benzyl glycidyl ether and 4-hydroxybutyl (meth) acrylate glycidyl ether are especially preferable. Vinylbenzyl glycidyl ether is a compound represented by following General formula (3), and can improve heat resistance and chemical-resistance.

[Equation 3]

On the other hand, 4-hydroxybutyl (meth) acrylate glycidyl ether is preferably used to increase the sensitivity.

The carboxylic acid reactive compound is added to the high molecular compound. In the photosensitive resin of the present invention, the ratio of the carboxylic acid reactive compound varies depending on the use, but cannot be uniformly used. However, when applied to the use of alkali developability, the acid value of the resin solid content is 30 to 150 mg gOH / H. It is preferable to adjust so that it exists in the range of g. When the acid value is too low than 30 mggOH / g, the developing speed may decrease and a required pattern may not be obtained. On the other hand, when an acid value is higher than 150 mggOH / g, it may become overdevelopment and a pattern will peel easily, and electrical characteristics etc. may fall. 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. Since the kind of catalyst differs according to the kind of carboxylic acid reactive compound, it cannot be said uniformly, For example, 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 Amines such as [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] nonen-5, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetra Quaternary ammonium compounds such as methyl ammonium hydroxide, 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, The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of compounds (1). When the amount of the catalyst is too large, it may adversely affect the electrical characteristics and storage stability of the photosensitive resin.

Moreover, when making a carboxylic acid reactive compound react, it is preferable to add a polymerization inhibitor. There is no restriction | limiting in particular in the kind of polymerization inhibitor as long as it suppresses reaction of an unsaturated bond, As an example, hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butyl T-butylcatechol, N-methyl-N-nitrosoaniline or N-nitrosophenylhydroxylamine (ammonium salt of N-nitrosophenyl hydroxylamine) Industrial Co., Ltd. product: Q-1300), N-nitrosophenylhydroxylamine aluminum salt (product of Wako Pure Chemical Industries, Ltd .: Q-1301), 2,2,6,6-tetramethylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidine-1-oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-2,2,6,6 -tetramethylpiperidine-1-oxyl) etc. are mentioned. In particular, N-nitrosophenyl hydroxylamine aluminum salt and 4-hydroxy-2,2,6,6- tetramethyl piperidine-1-oxyl are preferable. Although the quantity of a polymerization inhibitor differs according to the kind and reaction conditions, although it cannot speak uniformly, the range of 5-2000 mm is preferable with respect to the whole photosensitive resin. When less than this range, unsaturated bond may react and gelation may arise during manufacture, and when more than this range, since sensitivity may fall, it is unpreferable.

When adding a carboxylic acid reactive compound, it is preferable to heat for the purpose of the improvement of reaction rate. Although heating temperature can be set suitably according to the kind and apparatus of a carboxylic acid reactive compound, the range of 60-150 degreeC is generally preferable. When reaction temperature is lower than 60 degreeC, it may take time until completion | finish of reaction. On the other hand, when reaction temperature is higher than 150 degreeC, side reactions, such as coloring, may occur, or an unsaturated bond may react and gelatinization may occur.

In the polymer compound obtained by reacting the compound (1) with the compound (2), in the case of the above-described mixing ratio, since the compound (2) is excessive with respect to the compound (1), the polymer terminal has a structure of an acid anhydride. . In the case where an epoxy compound having an ethylenically unsaturated group is used as the carboxylic acid reactive compound, an acid anhydride may react with the -OH group produced by the ring-opening of an epoxy ring to cause an increase in molecular weight. In order to suppress the molecular weight increase by this reaction, it is preferable to make the compound or water which has a hydroxyl group represented by following General formula (6) react with the acid anhydride structure part of a polymer terminal.

[Equation 6]

(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).)

[Equation 7]

(In the formula, l, p, q each independently represent an integer of 0 to 9. However, l, p, q do not become 0 at the same time.)

Such a reaction may be made prior to or simultaneously with addition of an epoxy compound having an ethylenically unsaturated group, but in view of the reproducibility of the reaction, it is more preferable to be made prior to the reaction of the epoxy compound having an ethylenically unsaturated group.

As a compound represented by the said General formula (6) (Hereinafter, it may be called "compound (6).), Specifically, 2-hydroxyethyl (meth) acrylate (2-hydroxyethyl methacrylate), 2- 2-hydroxypropyl methacrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (4-hydroxybutyl methacrylate), 6-hydroxyhexyl (meth ) Acrylate (6-hydroxyhexyl methacrylate), 9-hydroxynonyl (meth) acrylate (9-hydroxynonyl methacrylate) and the like can be exemplified, among these in terms of crosslinking reactivity and cost, 2-hydroxyethyl acrylate , 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate are preferably used.

A catalyst may be used when the compound (6) or water is reacted. The type of catalyst is the same as that which can be used in the reaction of the compound (1) and the compound (2), and may be used as it is in this reaction or may be the same or additionally added another kind of catalyst. The reaction temperature is preferably in the range of 60 to 150 ° C. When reaction temperature is too low, it may take time until completion | finish of reaction. When reaction temperature is too high, side reactions, such as coloring, may occur, or an unsaturated bond may react and gelatinization may occur.

The photosensitive resin prepared as mentioned above is spray drying, film drying, dropping to a poor solvent, reprecipitation for the purpose of refine | purification, preservation, a solvent change, etc. V) and the like, and may be taken as a solid.

Although the molecular weight of the photosensitive resin of this invention is not specifically limited, 1,500-100,000 are preferable and 2,000-20,000 are more preferable. If it is this range, the balance of coating film strength and developability is favorable, and it is preferable. In this specification, the molecular weight of photosensitive resin is the styrene conversion weight average molecular weight by GP of the conditions described in the Example.

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

Although it does not restrict | limit especially as a photoinitiator and / or a photosensitizer used for this invention, For example, benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethyl Bis-N, N-dimethylamino benzophenone, bis-N, N-diethylamino benzophenone, 4-methoxy-4'-dimethylaminobenzophenone (4 benzophenones such as -methoxy-4'-dimethylamino benzophenone, thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone and chlorothione Thioxanthones such as oxanthone, isopropoxychlorothioxanthone, ethylanthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone, and chloroanthraquinone Anthraquinone-2-sulfonate (a Anthraquinones such as nthraquinone-2-sulfonate, anthraquinone-2,6-disulfonate, anthraquinones, acetophenones, and benzoin methyl ether ), Benzoin ethers such as benzoin ethyl ether and benzoin phenyl ether, 2,4,6-trihalomethyltriazines (2,4,6) -trihalomethyl triazines), 1-hydroxycyclohexylphenylketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole duplex (2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer), 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole duplex (2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimmer), 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex (2- (o-fluorophenyl) -4,5-diphenylimidazole dimer), 2- (o-methoxyphenyl ) (4,5-diphenylimidazole dimer) (2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer), 2- (p-methoxyfe Yl) -4,5-diphenylimidazole duplex, 2,4-di (p-methoxyphenyl) -5-phenylimidazole duplex (2,4-di (p-methoxyphenyl) -5- 2,4, such as phenylimidazole dimer) and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole duplex (2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimmer) , 5-triarylimidazole dimer, benzyl dimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone (2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy -2-methyl-1-phenyl-propan-1-one), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one ( 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one), 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)] (1- [4- (phenylthio) -, 2- (o-benzoyloxime)]), phenanthrenequinone (phenanthrenequinone), 9,10-phenanthrenequinone (9,10-phenanthrenequinone), methylbenzoin (methylbenzoin), ethylbenzoin (ethylbenzoin) acridine derivatives such as (benzoins), 9-phenylacridine, 1,7-bis (9,9-acridinyl) heptane (1,7-bis (9-acridinyl) heptane) acridine derivative) and bisacylphosphine oxide ((bis) acylphosphine oxide), and one or two or more thereof can be used.

An accelerator may also be added to the photosensitive resin of the present invention. Examples of accelerators include p-dimethylamino ethyl-benzoate, p-dimethylamino isoamyl-benzoate, and N, N-dimethylethanolamine ), N-methyldiethanolamine, triethanolamine and the like.

In the photosensitive resin composition of the present invention, a polymerizable monomer (hereinafter, simply referred to as a "polymerizable monomer") having one or more unsaturated groups in the molecule can be further used, whereby sensitivity, chemical resistance, Heat resistance and mechanical strength can be improved. Moreover, a polymerizable monomer can also be added for the purpose of adjusting a flow characteristic. As this polymerizable monomer, if it has one or more unsaturated bonds in a molecule | numerator, it can be used without a restriction | limiting in particular, What is necessary is just to select a suitable thing according to the use and the objective to apply. For example, polyethylene glycol di (meth) acrylate (the number of ethylene groups is 2 to 14), trimethylolpropanedi (meth) acrylate (trimethylolpropane di (meth) ) acrylate), trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy tri (meth) acrylate, trimethylolpropane propoxytri ( Trimethylolpropane propoxy trimethacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene Polypropylene glycol di (meth) acrylate (the number of propylene groups is 2-14), dipentaerythritol penta (meth) acrylate Dipentaerythritol 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 deoxyoxydi (meth) acrylate (Meth) acrylate (bisphenol A decaoxyethylene di (meth) acrylate), polyhydric carboxylic acid (phthalic anhydride, etc.), a compound having a hydroxyl group and an ethylenically unsaturated group (β-hydroxyethyl ( Esterified compounds with meth-acrylate (ß-hydroxyethyl (meth) acrylate), (meth) acrylic acid methyl ester, (meth) acrylate ethyl ester (methacryli) (meth) acrylic acid alkyl esters such as c acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester , Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether Tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether ether), tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl Of epoxy compounds such as terpropylene (tetrapropylene glycol diglycidyl ether), polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether, and glycerin triglycidyl ether Unsaturated organic acids such as metaacrylic acid adduct and maleic acid and their anhydrides, N-methylacrylamide, N-ethylacrylamide, N-isopropyl N-isopropylacrylamide, N-methylolacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacryl N-isopropylmethacrylamide, N-methylolmethacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide acrylamides such as -diethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, styrene, hydroxystyrene styrenes such as (hydroxystyrene), N-vinylpyrrolidone, N-vinyl formamide, N-vinyl acetamide, and N-vinylimidazole (N-vinyl imidazole) etc. can be illustrated, and 1 type, or 2 or more types thereof can be used.

A coloring agent can also be added to the photosensitive resin composition of this invention for the purpose of designability, visibility, antihalation of a photoresist, etc. The type of coloring agent to be added can be appropriately selected depending on the purpose of coloring, and for example, phthalocyanine dyes, anthraquinone dyes, azo dyes, and indigo dyes. dyes, coumarin dyes, triphenylmethane dyes, phthalocyanine pigments, anthraquinone pigments, azo pigments, quinacridone pigments (quinacridone pigments), coumarin pigments (coumarin pigments), triphenylmethane pigments (triphenylmethane pigments) and the like can be exemplified, one or two or more thereof can be used.

The photosensitive resin composition of this invention can be in the form of a solution or a paste, and may contain a solvent for this. Although there is no restriction | limiting in particular in the kind of solvent used, As an example, Ethylene glycol, such as water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc. Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether, and ethylene glycol monoethyl ether acetate Glycol ether acetates such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol , Propylene Glycol Monome 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 ethers such as propylene glycol diethyl ether and dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like. Acetone, such as propylene glycol ether acetates, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, lactic acid esters such as methyl lactate and ethyl lactate, ethyl acetate and butyl acetate There may be mentioned esters, dimethyl sulfoxide, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

In the photosensitive resin composition of this invention, further conventionally well-known components, such as a polymerization inhibitor, a plasticizer, an antifoamer, and a coupling agent, can be further mix | blended as needed.

The photosensitive resin composition of this invention can be obtained by mixing a solvent and other optional components according to the above-mentioned essential component and if necessary according to a normal method.

The photosensitive resin composition of this invention obtained as mentioned above can be used for the use of photoresists, such as a liquid crystal color filter, a black matrix, and a soldering resist. When used as a photoresist, the photosensitive resin composition of this invention is apply | coated on a board | substrate as a solution or a paste. The coating method is not particularly limited, but screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, A slit coat or the like is applied. The coated solution or paste is exposed to light by a thin film or an electron beam with a predetermined mask therebetween. When apply | coating using a solvent, you may go through a drying process. A pattern can be formed by wet-developing the exposed coating film. The developing method may be any of spray method, paddle method, immersion method, and the like, but a spray method containing few residues is preferable. If necessary, ultrasonic waves or the like can also be irradiated. As the developing solution, it is preferable to use alkalescent water. It is also possible to add an organic solvent, a surfactant, an antifoaming agent and the like for the purpose of developing assistance.

(Example)

Although an Example demonstrates this invention in detail below, this invention is not limited at all by these.

Example 1

In a 1000 ml flask equipped with a stirrer and a cooling tube, pyromellitic acid 2 anhydride (manufactured by Daicel Chemical Industries, Ltd .: PMDA) 67.5 g, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemicals Co., Ltd. product: 82.5 g of JPPE) and 100 g of propylene glycol monomethyl ether acetate were added thereto, and the mixture was stirred under a nitrogen stream. Heated at 155 ° C. in an oil bath for 4 hours. Subsequently, after cooling to 120 degreeC, 0.9 g of 4-dimethylamino pyridine, 4-hydroxy-2,2,6,6- tetramethyl piperidine- 1-oxyl (made by ADEVA: ADADESTAB (ADK STAB) ) 0.07 g of LA-7RD) and 30.0 g of 2-hydroxyethyl acrylate were added, and stirring was continued at 120 degreeC for 4 hours. Furthermore, 75.0 g of 4-vinyl benzyl glycidyl ether was added, and it stirred at 120 degreeC for 2 hours. Next, it cooled to room temperature and propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the pale yellow transparent viscous photosensitive resin (A1) solution was obtained.

About the obtained resin solution, when the viscosity, the styrene conversion weight average molecular weight by WPC, and solid content acid value were measured, it was 420 mPas / 25 degreeC and styrene conversion weight average molecular weight 5,330 by WPC, and solid content acid value 52.0 mg gOH / g. For viscosity measurement, a MM type viscometer manufactured by Dong-Kyo Industry Co., Ltd. was used. In addition, the measurement of GPC was carried out by THS eluent 40 degreeC and 0.5 ml / mI flow rate using the THS Corporation G7000HVL and the TSVELHEL G2500HVL manufactured by Tosoh Corporation, and the TSGELEL G2500HVL on the column. The acid value was measured in accordance with the neutralization titration method described in JIS-K0070.

Example 2

Except for changing 75.0 g of 4-vinyl benzyl glycidyl ether to 81.0 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd .: 4HWAHA) A photosensitive resin (A2) solution of a pale yellow transparent viscous liquid was obtained in the same manner as 1. The solution was analyzed in the same manner as in Example 1, and the viscosity was 330 mPa · s / 25 ° C., a styrene reduced weight average molecular weight of 4,920 and a solid acid value of 54.8 mg gOH / g.

Example 3

In a 1000 ml flask equipped with a stirrer and a cooling tube, 67.5 g of biphenyltetracarboxylic acid dianhydride (manufactured by UBungsan Co., Ltd .: BPDA), 9,9-bis [4- (2-hydroxyethoxy) 82.5 g of phenyl] fluorene (the product made by OSAKA Chemical Co., Ltd .: WEPE), 0.9 g of 4-dimethylaminopyridine, and 100 g of propylene glycol monomethyl ether acetate were added, and it heated in 155 degreeC oil bath for 4 hours, stirring under nitrogen stream. Subsequently, after cooling to 120 degreeC, 4-hydroxy-2,2,6,6- tetramethyl piperidine- 1-oxyl (made by ADEVA: Adecastab LA-7RD) 0.03g, 2-hydroxy 12.0 g of ethylacrylate were added and stirring was continued at 120 ° C. for 4 hours. 42.0 g of 4-vinyl benzyl glycidyl ether was further added, and it stirred at 120 degreeC for 2 hours. Next, it cooled to room temperature and propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the light brown transparent viscous photosensitive resin (A3) solution was obtained. The solution was analyzed in the same manner as in Example 1, and a viscosity of 2860 mPa · s / 25 ° C. and a styrene reduced weight average molecular weight of 6,610 and a solid acid value of 65.2 mggOH / g was determined by PPC.

Example 4

The reaction mixture was carried out under the same conditions as in Example 3 except that 42.0 g of 4-vinyl benzyl glycidyl ether was changed to 45.0 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nihon Kasei Co., Ltd .: 4HWAHAE). The liquid photosensitive resin (A4) solution was obtained. When the solution was analyzed in the same manner as in Example 1, the viscosity was 990 mPa · s / 25 ° C., the weight average molecular weight 6,200 in terms of styrene by PPC and the solid acid value 64.5 mg gOH / g.

Example 5

Into a 1000 ml flask equipped with a stirrer and a cooling tube, 75 g of biphenyltetracarboxylic acid dianhydride (manufactured by Ubo Chemical Co., Ltd .: JPDA), ethylene oxide adduct of bisphenol A (Japan Emulsifier Co., Ltd.) Co., Ltd. product: 75 g of BA2 glycol), 0.9 g of 4-dimethylaminopyridine, and 100 g of propylene glycol monomethyl ether acetate were added thereto, and the mixture was heated in an oil bath at 155 ° C. for 4 hours while stirring under a nitrogen stream. Subsequently, after cooling to 120 degreeC, 4-hydroxy-2,2,6,6- tetramethyl piperidine- 1-oxyl (made by ADEVA: Adecastab LA-7RD) 0.03g, 2-hydroxy 6 g of ethylacrylate was added and stirring was continued at 120 ° C. for 4 hours. 51 g of 4-vinylbenzyl glycidyl ether was further added, and the mixture was stirred at 120 ° C for 2 hours. Next, it cooled to room temperature and propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the pale yellow transparent viscous photosensitive resin (A5) solution was obtained. The solution was analyzed in the same manner as in Example 1, and the viscosity was 1960 mPas / 25 ° C, styrene reduced weight average molecular weight 12,470 by PPC, and solid acid value 69 mggOH / g.

Example 6

Except for changing 51 g of 4-vinyl benzyl glycidyl ether to 54 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nihon Kasei Co., Ltd .: 4HWAHA), the reaction was carried out under the same conditions as in Example 5 to obtain a pale yellow transparent viscous liquid. The photosensitive resin (A6) solution was obtained. The solution was analyzed in the same manner as in Example 1, and the viscosity was 1430 mPa · s / 25 ° C., a styrene reduced weight average molecular weight of 14,200 using a PCC, and a solid acid value of 68.5 mg gOH / g.

Comparative Example 1

Patent document 3 (JP-A-9-325494) using bisphenol fluorene type epoxy resin (product of Osaka Chemical Co., Ltd .: PFF) of weight per epoxide equivalent 257 Photosensitive resin (A7) was obtained according to Synthesis Example 1 and Example 1 of the disclosure. Synthesis took 20 hours or more, and productivity was remarkably low compared with Examples 1-4 of this invention.

Comparative Example 2

Synthesis example 1 and Example 2 described in patent document 3 (Unexamined-Japanese-Patent No. 9-325494) using the bisphenol fluorene type epoxy resin of Epoxy equivalent 257 (made by Osaka Chemical Co., Ltd .: PFP). Thus, photosensitive resin (A8) was obtained. Synthesis took 21 hours or more, and productivity was remarkably low compared with Examples 1-4 of this invention.

Comparative Example 3

Except for changing 42.0 g of 4-vinyl benzyl glycidyl ether to 18.0 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd .: XAM) under the same conditions as in Example 3. It reacted and obtained the photosensitive resin (A9) solution of the pale yellow transparent viscous liquid. When the solution was analyzed in the same manner as in Example 1, the viscosity was 8,100 mPa · s / 25 ° C, the weight average molecular weight of 5,200 in terms of styrene by PPC, and the solid acid value was 86.5 mggOH / g.

Comparative Example 4

A photosensitive resin of a pale yellow transparent viscous liquid was reacted under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was changed to 21.1 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.). A10) A solution was obtained. When the solution was analyzed in the same manner as in Example 1, the viscosity was 7,800 mPas / 25 ° C, the weight average molecular weight 6,500 in terms of styrene in terms of PCC, and the solid acid value was 75.6 mggOH / 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 the PPC immediately after manufacture and 1 month after room temperature storage was measured, and the change rate was investigated.

The results are shown in Table 1.

Almost no change was observed in the photosensitive resins of Examples 1 to 6, but the photosensitive resins of Comparative Examples 1 and 2 showed an increase in molecular weight of about 25%, indicating poor storage stability.

Example 7

Using the photosensitive resin A1 obtained in Example 1, the photosensitive resin composition was prepared by the formulation shown in Table 2 below. The photosensitive resin composition was applied to a soda-lime glass plate having a thickness of 1.1 mm by a spin coater so as to have a dry film thickness of 3 μm and 90 seconds on a 100 ° C. hot plate. After drying, it was cooled to room temperature. Subsequently an extra-high pressure mercury lamp exposure machine (超高壓水銀燈露光機) ultraviolet illumination 15mW / cm ² (365nm), cumulative dose 20mJ / to ^{cm 2, UGRA-OFFSET-TEST} KAIL1982 a soft contact exposure (soft contact exposure) a as a mask by After that, a pattern was formed by immersion in 1% sodium carbonate water at 25 ° C. for 90 seconds to form a pattern, and the sensitivity was evaluated by the microline with the remaining step number. The results are shown in Table 2 together.

Examples 8-10 and Comparative Examples 5-8

Except having changed photosensitive resin A1 into photosensitive resin A2-A10, it carried out similarly to Example 7, and prepared the photosensitive resin composition, and evaluated the sensitivity and the resolution. The results are shown in Table 2 together.

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 showed favorable resist characteristic.

The photosensitive resin of the present invention is not only excellent in chemical resistance and heat resistance, but also high in productivity and excellent in storage stability. Since the photosensitive resin composition using the same has high sensitivity and good patterning property, It is used suitably for the use of a resist.

Claims (9)

Carboxylic acid reactive compound which has an ethylenically unsaturated group in the high molecular compound obtained by making the compound represented by following General formula (1) react with the compound represented by following General formula (2). Photosensitive resin obtained by the addition of carboxylic acid.
[Equation 1]

Wherein Y is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, cyclo Hexyl group (cyclohexyl group), 9,9-fluorenyl group (9,9-fluorenyl group) or a direct bond, R ¹ , R ² independently represent a hydrogen atom or a methyl group, n, m is independently 0 The number of -4 is shown.)

[Formula 2]

(Where X represents a tetravalent carboxylic acid residue)
The method of claim 1,
The ratio of the compound represented by General formula (2) with respect to 100 mol part of compounds represented by General formula (1) is 110-200 mol part, The photosensitive resin characterized by the above-mentioned.
The method according to claim 1 or 2,
The carboxylic acid reactive compound which has an ethylenically unsaturated group is represented by following General formula (3), Photosensitive resin characterized by the above-mentioned.
[Equation 3]

4. The method according to any one of claims 1 to 3,
The carboxylic acid reactive compound which has an ethylenically unsaturated group is represented by following General formula (4), Photosensitive resin characterized by the above-mentioned.
[Equation 4]

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a group represented by the following General Formula (5))
[Equation 5]

(In the formula, r, s, and t each independently represent an integer of 0 to 9. However, r, s, and t never become 0 at the same time.)
5. The method according to any one of claims 1 to 4,
The compound represented by following General formula (6) or water is further added to the high molecular compound obtained by making the compound represented by General formula (1) react with the compound represented by General formula (2), The photosensitive resin characterized by the above-mentioned.
[Equation 6]

(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).)
[Equation 7]

(In the formula, l, p, q each independently represent an integer of 0 to 9. However, l, p, q do not become 0 at the same time.)
The method according to any one of claims 1 to 5,
X in General formula (1) is a 9, 9- fluorenyl group, Photosensitive resin characterized by the above-mentioned.
The method according to any one of claims 1 to 6,
The acid value is 30-150 mggOH / g, The photosensitive resin characterized by the above-mentioned.
The photosensitive resin of any one of Claims 1-7 and a photoinitiator and / or a photosensitizer are included, The photosensitive resin composition characterized by the above-mentioned.
The method of claim 8,
The photosensitive resin composition characterized by further containing the polymerizable monomer which has one or more unsaturated groups in a molecule | numerator.