JP2010084144A - Base generator and photosensitive resin composition comprising base generator - Google Patents

Abstract

[PROBLEMS] To provide a base generator having a high base strength and a base generating reaction that is performed in a chain when applied to an epoxy compound and the like, and a photosensitive resin containing the base generator. Providing a composition.
[Solution]
The base generator of the present invention is a carboxylic acid salt composed of a predetermined carboxylic acid and an alkali metal or alkaline earth metal, amidine or imidazole, guanidine or phosphazene derivative. The basicity is high due to the generation of strong alkali by the action of water, and the reaction efficiency is excellent. In the case where the photosensitive resin composition is constituted together with the base-reactive compound, the reaction between the base generated from the base generator and the epoxy compound proceeds in a chain, and the curing is promptly performed even at the room temperature level. Since it becomes a photosensitive resin composition that is sufficiently cured by being implemented, it can be suitably used for, for example, a highly sensitive photocuring material or resist material.
[Selection] Figure 1

Description

  The present invention relates to a base generator and a photosensitive resin composition containing the base generator. More specifically, the present invention relates to a base generator that generates a base by active energy rays such as light and a photosensitive resin composition containing the base generator.

  A photosensitive resin composition containing an acid generator that generates an acid upon irradiation with light is applied as a photoresist material, a photocuring material, or the like. The acid generated from the acid generator acts as a catalyst or a polymerization initiator. When a photosensitive resin composition containing an acid generator or the like is used as a photoresist material to form a pattern, for example, acid generation The agent is irradiated with light to generate a strong acid serving as a catalyst, and the resin component is chemically modified. Then, a pattern is formed by the change in solubility of the chemically modified resin component.

  Such a photoresist material is required to have a high resolution and sensitivity and to be able to form a pattern with high etching resistance. In particular, as a deep ultraviolet resist material, a pattern resistant to oxygen plasma etching is formed. There is a need for materials that can be used. Various photoresist materials comprising a photosensitive resin composition containing an acid generator have been provided for the purpose of high sensitivity, high resolution, etc., but a combination of a photoacid generator and a resin material is provided. Since the types are limited to some extent, a new photosensitive system that does not use an acid generator has been demanded.

  In addition, various studies have been made to improve the photocuring speed of monomers, oligomers, or polymers, and radical photopolymerization systems that polymerize many vinyl monomers using radical species generated by the action of light as initiators. These materials have been widely targeted for development. In addition, active studies have been made on cationic polymerization materials that generate an acid by the action of light and use this acid as a catalyst. However, in the case of radical photopolymerization-type materials, since the polymerization reaction is inhibited and the curing reaction is suppressed by oxygen in the air, a special device for blocking oxygen has been required. In addition, in the case of a cationic polymerization material, there is no oxygen inhibition like a radical photopolymerization material, but the strong acid generated from the photoacid generator remains after curing, which causes the presence of the strong acid. The corrosivity and the possibility of denaturation of the resin have been problems.

  Against this background, in order to obtain a resist material that can form a pattern with high resolution and sensitivity and high etching resistance, a curing technology that rapidly solidifies a liquid substance using active energy rays is further improved in performance. Therefore, a photosensitive resin composition using a new photosensitive system that is not affected by oxygen in the air and does not contain corrosive substances such as strong acids that are generated and that has a highly efficient reaction is strong. It was desired.

  As one of the means for overcoming the above problems, a method using a polymerization reaction or chemical reaction by a base catalyst, for example, a method of generating a base by the action of light and chemically denaturing a resin using this as a catalyst, A means for applying a photosensitive resin composition using a base generated by the above as a catalyst to a photoresist material, a photocuring material or the like has been studied. The compound having an epoxy group is cured by causing a crosslinking reaction by the action of a base to generate amines as initiators or catalysts in the epoxy resin layer by the action of light or heat, and then heated. Methods of curing by treatment are provided (see, for example, Patent Document 1 and Patent Document 2).

JP 2005-264156 A Japanese Patent Laid-Open No. 2007-10185

  However, in the methods provided in the past, there is a problem in that there is a limitation in the intensity of the base that can be generated, and there is a problem that the reaction for generating the base by the action of light is not performed quickly. It was poor in nature and required improvement.

  The present invention has been made in view of the above-mentioned problems, and can be used for, for example, a crosslinking reaction of an epoxy compound, the strength of a generated base is high, and when applied to an epoxy compound or the like, It is an object of the present invention to provide a base generator excellent in reaction efficiency and a photosensitive resin composition containing the base generator in which base generation reactions are performed in a chain.

  In order to solve the above-mentioned problems, the base generator according to the first invention of the present invention is a carboxylic acid salt composed of a carboxylic acid and an alkali metal or an alkaline earth metal, and is represented by the following formula (X): It is characterized by.

（式（Ｘ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｍはアルカリ金属またはアルカリ土類金属、ｎは１または２の整数、を示す。）

(In the formula (X), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ each represent a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, M represents an alkali metal or an alkaline earth metal, and n represents an integer of 1 or 2. )

  The base generator according to the second aspect of the present invention is a carboxylic acid salt composed of a carboxylic acid (excluding ketoprofen) and a base, and is represented by the following formula (Y).

（式（Ｙ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｑは下記式（Ｉ）で表されるアミジン類、式（II）で表されるイミダゾール類、のいずれかからなる塩基類、を示す。）

(In the formula (Y), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, Q is an amidine represented by the following formula (I), and a formula (II). Bases consisting of any of the following imidazoles):

（式（Ｉ）中、ｎは１〜３の整数を示す。）

(In formula (I), n represents an integer of 1 to 3)

（式（II）中、Ｒはそれぞれ、独立して水素原子、炭素数が１〜４のアルキル基（Ｓ等のヘテロ原子を含んでもよい。）、またはフェニル基、を示す。）

(In formula (II), each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (which may contain a heteroatom such as S), or a phenyl group.)

  The base generator according to the third aspect of the present invention is a carboxylic acid salt composed of a carboxylic acid and a base, and is represented by the following formula (Z).

（式（Ｚ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｇは下記式（IV）で表されるグアニジン類、式（Ｖ）で表されるホスファゼン誘導体、のいずれかからなる塩基類、を示す。）

(In the formula (Z), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, G is a guanidine represented by the following formula (IV), and a formula (V). A phosphazene derivative, a base consisting of any one of

（式（IV）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (IV), R _{1 to} R ₅ each independently represents a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（Ｖ）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (V), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

  The base generator according to the present invention is characterized in that, in the first invention or the third invention, the carboxylic acid is ketoprofen.

  A photosensitive resin composition according to the present invention comprises the base generator according to any one of the first to third inventions and a base-reactive compound.

  The photosensitive resin composition according to the present invention is characterized in that, in the photosensitive resin composition, the base reactive compound is an epoxy compound and / or a silicon compound.

  Since the base generator according to the first invention of the present invention is a carboxylate composed of a predetermined carboxylic acid and an alkali metal or alkaline earth metal as a base, it is decarboxylated by light, and as a result, in the air A strong alkali is generated by the action of water, so that the basicity is high (acid dissociation constant (pKa) is approximately 13 or more (water solvent)), the reaction efficiency is excellent, and the photosensitive resin composition is constituted with a base-reactive compound. In this case, the reaction with a base-reactive compound such as an epoxy compound proceeds in a chain, and becomes a base generator with a remarkably high reaction efficiency with the compound.

  Since the base generator according to the second invention of the present invention is a carboxylate composed of a predetermined carboxylic acid (excluding ketoprofen) and an amidine or imidazole as a base, it is decarboxylated by light, and the result Since it produces free amidine or imidazole, its basicity is high (acid dissociation constant (pKa) is about 12 to 13 (aqueous solvent)), it is excellent in reaction efficiency like the first invention, and is photosensitive with a basic reactive compound. In the case of constituting a resin composition, the reaction with a base-reactive compound such as an epoxy-based compound proceeds in a chain, and becomes a base generator with a remarkably high reaction efficiency with the compound.

  Since the base generator according to the third invention of the present invention is a carboxylate composed of a predetermined carboxylic acid and a guanidine or phosphazene derivative as a base, it is decarboxylated by light, and as a result, free guanidine or Since the phosphazene derivative is formed, the basicity is high (acid dissociation constant (pKa) exceeds 13.5 (aqueous solvent), and the reaction efficiency is excellent as in the first and second inventions. In the case of constituting a functional resin composition, the reaction with a base-reactive compound such as an epoxy compound proceeds in a chain, and becomes a base generator with a remarkably high reaction efficiency with the compound.

In addition, the base generator according to the third invention of the present invention employs guanidines and the like as the bases. In general, the basicity of amines and amidines is 10 (amine) to 24 (amidines) of pKa (pKa of conjugate acid, acetonitrile (in CH ₃ CN solvent)). While anionic ring-opening polymerization of siloxane hardly occurs, in guanidines and phosphazene derivatives, pKa becomes about 26 to 27 (in acetonitrile (CH ₃ CN) solvent) and anion ring-opening polymerization occurs. Since it changes to a polymer by the reaction, it is most suitable as a base generator applied to lactones which are base reactive compounds. Moreover, the obtained photosensitive resin compound can also be used as photocuring materials (UV adhesion, UV ink, UV adhesion, UV coating, etc.).

  Since the base generator according to the present invention employs ketoprofen as the carboxylic acid in the first or third invention described above, the quantum yield of ketoprofen is the highest among the carboxylic acids that cause photodecarboxylation ( Φ = 0.75) and can be expected to function as an extremely efficient base generator.

  Since the photosensitive resin composition according to the present invention contains the base generator of the present invention and a base reactive compound, the reaction between the base generated from the base generator and the epoxy compound is chained. Since it progresses and has excellent reaction efficiency, it is a photosensitive resin composition that is rapidly cured even at a room temperature level and is sufficiently cured. The photosensitive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material, and the like.

  Since the photosensitive resin composition according to the present invention employs an epoxy compound or a silicon compound as a base-reactive compound constituting the resin composition, curing is carried out efficiently. When a compound or a polymerizable silicon-based compound is employed, a polymer obtained by ring-opening polymerization of an epoxy group or condensation polymerization of a silanol group or an alkoxysilyl group can be suitably provided. In addition, since epoxy compounds and the like are general-purpose materials, they are advantageous in terms of cost.

FIG. 3 is a view showing the photodegradation behavior (wavelength: 254 nm) of the base generator obtained in Example 1. It is the figure which showed the photodegradation behavior (wavelength: 313 nm) of the base generator obtained in Example 1. In Experiment 1, it is the figure which showed the relationship (temperature dependence) of the exposure amount and the remaining film rate. In Experiment 2, it is the figure which showed the relationship (time dependence) of the exposure amount and the remaining film rate. In Experiment 3, it is the figure which showed the relationship (density dependence) of the exposure amount and the remaining film rate. In Test Example 4, a diagram showing the relationship between the amount of exposure time and SiO _2. In Experiment 5, it is the figure which showed the relationship (density dependence) of the exposure amount and the remaining film rate.

  Hereinafter, one embodiment of the present invention will be described. The base generator according to the first aspect of the present invention is a compound represented by a carboxylic acid salt composed of carboxylic acid and an alkali metal or alkaline earth metal M and represented by the following formula (X).

（式（Ｘ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｍはアルカリ金属またはアルカリ土類金属、ｎは１または２の整数、を示す。）

(In the formula (X), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ each represent a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, M represents an alkali metal or an alkaline earth metal, and n represents an integer of 1 or 2. )

The base generator of the first invention uses an alkali metal or an alkaline earth metal as a binding target with the carboxylic acid, and causes decarboxylation by irradiation with light, as shown in the following scheme 1. generating a strong alkali by the action of water in the (M ⁺ OH ^- OH medium ^- is a base generator which acts as a strong base.).

(Scheme 1)

  The base generator according to the second invention of the present invention is a compound represented by a carboxylic acid salt represented by the following formula (Y), which comprises a carboxylic acid (excluding ketoprofen) and a base Q. .

（式（Ｙ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｑは下記式（Ｉ）で表されるアミジン類、式（II）で表されるイミダゾール類、のいずれかからなる塩基類、を示す。）

(In the formula (Y), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, Q is an amidine represented by the following formula (I), and a formula (II). Bases consisting of any of the following imidazoles):

（式（Ｉ）中、ｎは１〜３の整数を示す。）

(In formula (I), n represents an integer of 1 to 3)

（式（II）中、Ｒはそれぞれ、独立して水素原子、炭素数が１〜４のアルキル基（Ｓ等のヘテロ原子を含んでもよい。）、またはフェニル基、を示す。）

(In formula (II), each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (which may contain a heteroatom such as S), or a phenyl group.)

  The base generator of the second invention uses amidines or imidazoles as bases, and is decarboxylated by irradiation with light, and as a result, bases such as free amidines or imidazoles are generated. The scheme is as shown in the following scheme 2 (amidines) and scheme 3 (imidazoles).

(Scheme 2)

(Scheme 3)

  The base generator according to the third aspect of the present invention is a compound represented by a carboxylic acid salt composed of a carboxylic acid and a base G and represented by the following formula (Z).

（式（Ｚ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｇは下記式（IV）で表されるグアニジン類、式（Ｖ）で表されるホスファゼン誘導体、のいずれかからなる塩基類、を示す。）

(In the formula (Z), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, G is a guanidine represented by the following formula (IV), and a formula (V). A phosphazene derivative, a base consisting of any one of

（式（IV）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (IV), R _{1 to} R ₅ each independently represents a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（Ｖ）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (V), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

  The base generator of the third invention uses guanidines or phosphazene derivatives as bases, and is decarboxylated by irradiation with light, and as a result, a base such as free guanidines or phosphazene derivatives is generated. The scheme is as shown in the following scheme 2 '(guanidines) and scheme 3' (phosphazene derivatives).

(Scheme 2 ')

(Scheme 3 ')

  In the base generator of the present invention represented by the formula (X), (Y), or the formula (Z), Ar constituting the carboxylic acid is an aromatic ring, preferably an aryl group or a naphthyl group. Moreover, these aromatic rings can contain a benzoyl group, a nitro group, an alkoxy group, and an alkyl group as a substituent. It is preferable that carbon number of an alkoxy group and an alkyl group shall be 1-4. In addition, the substituent of this aromatic ring can take a ring structure.

  Further, R ′ and R ″ constituting the carboxylic acid are each a substituent such as a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group. It is preferable that carbon number of an alkoxy group and an alkyl group shall be 1-4.

  In the base generator of the first invention or the third invention of the present invention, examples of the target carboxylic acid include, for example, ketoprofen (2- (1-carboxyethyl) benzophenone represented by the following formula (III) .) Can be used. Among the carboxylic acids that cause photodecarboxylation, ketoprofen has the highest quantum yield (Φ = 0.75), and by using ketoprofen as the carboxylic acid, it functions as an extremely efficient base generator.

  In order to produce the base generator of the first invention represented by the formula (X), a compound containing a desired carboxylic acid and an alkali metal or alkaline earth metal M constituting a cation of a base (bases It can be easily produced by mixing methoxide, ethoxide, tert-butoxide and other compounds.

  Next, as M which comprises the base generator of 1st invention represented by Formula (X), an alkali metal and an alkaline-earth metal are mentioned. Examples of the alkali metal include sodium (Na) and potassium (K). Examples of the alkaline earth metal include calcium (Ca) and barium (Ba).

  The bases Q constituting the base generator of the second invention represented by the formula (Y) include amidines represented by the following formula (I) and imidazoles represented by the following formula (II). Can be mentioned.

（式（Ｉ）中、ｎは１〜３の整数を示す。）

(In formula (I), n represents an integer of 1 to 3)

（式（II）中、Ｒはそれぞれ、独立して水素原子、炭素数が１〜４のアルキル基（Ｓ等のヘテロ原子を含んでもよい。）、またはフェニル基、を示す。）

(In formula (II), each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (which may contain a heteroatom such as S), or a phenyl group.)

  Examples of amidines represented by formula (I) that can be used as bases include diazabicyclononene (DBN) represented by the following formula (Ia) having an amidine structure, and the following formula (I- and diazabicycloundecene (DBU) shown in b).

  Examples of the imidazoles represented by the formula (II) that can be used as the bases include imidazole, 1-methylimidazole shown in the following (II-a), and 2- in the following (II-b). Methylimidazole, 2-phenylimidazole, 3- (4,5-dihydro-2-imidazoyl) pyridine, 2-benzylimidazole, 4- (4,5-dihydro-1H-imidazol-2-yl) phenylamine, 3A, 4,5,6,7,7A-hexahydro-1H-benzimidazol-2-yl methyl sulfide, 2- (4-bromophenyl) 4,5-dihydro-1H-imidazole, 1- [3- (triethoxysilyl) ) Propyl] -4,5-dihydro-1H-imidazole, DL-isoamarin, etc. The existing alkyl group having 1 to 4 carbon atoms may contain a heteroatom such as S).

  In the base generator of the second invention represented by the formula (Y), ketoprofen (also referred to as 2- (1-carboxyethyl) benzophenone) represented by the formula (III) is not used as the carboxylic acid. .

  In order to produce the base generator of the second invention represented by the formula (Y), it is simply produced by mixing the desired carboxylic acid and the amidines or imidazoles to be generated, which are the bases Q. be able to.

The bases G constituting the base generator of the third invention represented by the formula (Z) include guanidines represented by the following formula (IV) and phosphazene derivatives represented by the following formula (V). Can be mentioned. Note that R _{1 to} R ₅ in formula (IV) and R _{1 to} R ₇ in formula (V) each independently represent a hydrogen atom, an alkyl group, or an aryl group (the alkyl group may be a cyclic structure). The alkyl group preferably has 1 to 4 carbon atoms.

（式（IV）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (IV), R _{1 to} R ₅ each independently represents a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（Ｖ）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (V), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

  Examples of the guanidine represented by the formula (IV) that can be used as the base include, for example, guanidine represented by the following formula (IV-a) having a guanidine structure, and 1, represented by the following formula (IV-b). 1,3,3-tetramethylguanidine (TMG), 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene (1,5,7-) represented by the following formula (IV-c) triaza-bicyclo [4.4.0] dec-5-ene: TBD), MTBD shown in (formula IV-d), ETBD shown in formula (IV-e), ITBD shown in formula (IV-f), formula Examples include compounds represented by the formula (IV-h) shown in (IV-g) (the formulas (IV-a) to (IV-h) represent proton adducts).

  Moreover, as a phosphazene derivative represented by the formula (V) that can be used as a base, the following formula (Va), formula (Vb), formula (Vc) or (Vd) And the like (the formula (Va) to the formula (Vd) represent proton adducts).

In order to produce the base generator of the third invention represented by the formula (Z), it is simply produced by mixing the desired carboxylic acid and the guanidine or phosphazene derivative to be generated, which becomes the base G. be able to.

  The base generator of the present invention is a compound (carboxylate) represented by the above formula (X), formula (Y) or formula (Z), but as a binding target of the carboxylic acid constituting the compound, Since a predetermined alkali metal, alkaline earth metal, amidine or imidazole, guanidine or phosphazene derivative is used, if the acid dissociation constant (pKa) is a base generator of the formula (X), it is approximately 13 or more ( In a water solvent), about 12 to 13 for a base generator of the formula (Y), and more than 13.5 for a base generator of the formula (Z) (both in a water solvent) (previously tertiary) Amine is about 10) It is very basic and acts as an excellent base generator with high reaction efficiency during polymerization. For example, when applied to an epoxy compound or the like, as shown in Scheme 5 and the like to be described later, the base deprives protons from water to generate hydroxide ions, which cause a chain polymerization reaction of the epoxy compound. Although the amount of hydroxide ions generated depends on the base strength, the higher the base strength, the higher the polymerization reaction efficiency. Furthermore, for example, No. described later. 2-1. The 2-7 base-reactive compound is a high molecular compound in which the α-position proton of the electron-withdrawing group is withdrawn to cause β-elimination and polarity conversion occurs. The proton extraction efficiency at this time also depends on the base strength. Therefore, the elimination reaction is more likely to occur as the base strength increases, and the photosensitive resin composition containing the base generator of the present invention can be expected to function as a highly sensitive photosensitive resin.

In general, the basicity of amines and amidines is pKa (pKa of conjugate acid, acetonitrile (in CH ₃ CN solvent) is 10 (amine) to 24 (amidines). While anionic ring-opening polymerization of cyclic siloxane hardly occurs, guanidines and phosphazene derivatives constituting the base generator according to the third invention represented by the formula (Z) have a pKa of about 26 to 27 (acetonitrile (CH ₃ CN ) In a solvent) and anionic ring-opening polymerization occurs, and when this is used, the monomer is converted into a polymer by a chain reaction. Therefore, the base generator according to the third invention is an optimal base generator for lactones, When applied to lactones, etc. to make photosensitive resin compositions, photo-curing materials (UV adhesion, UV ink, UV adhesive, UV coating, etc.) Can be applied to.

In addition, the range of the wavelength and exposure amount of the irradiation light in the base generator of the present invention and the photosensitive resin composition containing the base generator constitutes the type and amount of the base generator and the photosensitive resin composition. What is necessary is just to determine suitably according to the kind etc. of the base reactive compound to perform, For example, what is necessary is just to select from the range of 250-320 nm as a wavelength, and 100-1000 mJ / cm < ² > as an exposure amount, and to apply.

  Hereinafter, examples of the base generator of the present invention include alkali metals (sodium (Na), potassium (K)) and alkaline earth metals (calcium (Ca), barium (Ba)) as bases. Shown in 1 ′ to No 6-4 ′. When a divalent alkaline earth metal is used as the base, the formula (X) is represented by the following formula (X ′) (Ar, R ′, R ′ in the formula (X ′)) 'Is the same as the above-described formula (X).)

  Next, the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of this invention contains the base generator of this invention which decarboxylates with light and generate | occur | produces a free base, and a base reactive compound as an essential component. The base-reactive compound that constitutes the photosensitive resin composition of the present invention is a compound that reacts by the action of a base generated by a base generator and, if necessary, a base proliferating agent, and cures by crosslinking or the like. The following No. 2-1. 5-5 compounds and the like can be used. Particularly, for example, epoxy compounds having at least one epoxy group, silicon compounds having at least one alkoxysilyl group, silanol group, and the like can be mentioned. . Such base-reactive compounds may be used alone or in combination of two or more. Moreover, the base generator of this invention may be used individually by 1 type, and may be used in combination of 2 or more types.

  Hereinafter, the reaction behavior with the epoxy compound when the base generator of the present invention is applied will be described. In the following scheme, an amine is used for convenience as the base, and R and R ′ represent, for example, an alkyl group having 1 to 12 carbon atoms. It is not limited.

First, in the primary or secondary amine system, as shown in Scheme 4 below, for example, when a primary amine by a base generator is added to an epoxy group, it becomes an intermediate 1, but is eliminated as H ^+. Since there are two possible hydrogens on the nitrogen atom, one of them loses H ⁺ and changes to 2. On the other hand, since the changed 2 has the structure of a secondary amine, it can react with another epoxy compound once again to produce 3, but the produced 3 has the structure of a tertiary amine. However, it cannot react with the epoxy compound sterically. In addition, since the reaction proceeds as a sequential addition reaction, the epoxy compound is often not sufficiently cured.

(Scheme 4)

  On the other hand, when an alkali (alkali metal, alkaline earth metal) is used as a base as in the base generator of the first invention, the ring-opening reaction of epoxy proceeds in a chain manner as shown in Scheme 5 below. The reaction efficiency with the epoxy compound is remarkably increased.

(Scheme 5)

In addition, for tertiary amines and amidines such as the base generator of the second invention, imidazoles, guanidines such as the base generator of the third invention, and phosphazene derivatives, tertiary amines, amidines and imidazoles are used. , Guanidines, phosphazene derivatives and other bases may be added directly, and OH ⁻ may be generated from the base and water, and this may react with epoxy. When the base is directly added, compound 4 is first formed as shown in Scheme 6 below. In this case, since no hydrogen exists on the nitrogen atom, the charge on the oxygen atom does not disappear, It reacts with the following epoxy compound to produce 5. Thus, since the reaction with the epoxy compound proceeds in a chain manner, the reaction efficiency with the epoxy compound is remarkably higher than the addition reaction function such as the primary and secondary amine systems.

(Scheme 6)

On the other hand, when OH ⁻ is generated from a base and water and reacts with an epoxy, 6 is generated from the generated OH ⁻ as shown in the scheme 7 shown below. Does not disappear and reacts with the next epoxy compound to produce 7. Accordingly, the reaction with the epoxy compound proceeds in a chain as in the above-described scheme, and the reaction efficiency with the epoxy compound is remarkably increased.

(Scheme 7)

  Hereinafter, specific examples of the base-reactive compound will be given. In addition, the following No. 2-1. Among the 2-7 polymerized compounds (base-reactive compounds), No. 2-1. The polymer compound 2-5 undergoes elimination and decarboxylation by the action of a base. On the other hand, no. 2-6 and no. The 2-7 base-reactive compound causes a elimination reaction by the action of a base to produce a carboxylic acid.

  The above-mentioned base reactive compound No. 2-1. 2-7 is a polymer group that undergoes elimination reaction due to the action of a base and whose polarity is changed, and as a material (resist material) that performs patterning by utilizing the change in solubility before and after decomposition. Can be applied. Schemes of examples of decomposition mechanisms are shown in Scheme 8 and Scheme 9 below.

(Scheme 8)

(Scheme 9)

  Other examples of base-reactive compounds are also given. In addition, among the base reactive compounds No. 3-1 to No. 3-4 below, the substance (mixture) No. 3-1 undergoes dehydration condensation and crosslinking reactions by the action of the base. No. The substance (mixture) 3-2 causes dehydration condensation and crosslinking reaction by the action of the base. No. 3-3 substance (polymer) causes a decarboxylation reaction by the action of a base. The No. 3-4 substance causes an imide formation reaction by the action of a base. In addition, No. 3-1. In 3-2, x represents a number exceeding 0 and 1 or less.

  As the base-reactive compound constituting the photosensitive resin composition of the present invention, an epoxy compound having at least one epoxy group can be used. Moreover, an epoxy compound can be made into a polymer by ring-opening polymerization of an epoxy group by allowing a base to act on an epoxy compound having at least two epoxy groups. Moreover, such an epoxy compound can be chemically modified by adding a base to the epoxy compound. An example of an epoxy compound showing polymerization reactivity is shown below.

  Other examples of the epoxy compound (polymer) exhibiting polymerization reactivity are shown below.

  In addition, as the base-reactive compound, a silicon compound having at least one silanol group or alkoxysilyl group can be used. Further, by causing a base to act on a silicon compound having at least two silanol groups or alkoxysilyl groups, such a silicon compound can be made into a polymer by condensation polymerization of silanol groups or alkoxysilyl groups. Specific examples of silicon compounds showing polymerization reactivity (No. 5-2 to No. 5-4 are polymers) are shown below.

As described above, the guanidines and phosphazene derivatives constituting the base generator of the third invention represented by the formula (Z) have an pKa of about 26 to 27 (in acetonitrile (CH ₃ CN) solvent) and anions. Since ring-opening polymerization occurs, the monomer is converted into a polymer by a chain reaction. Therefore, a photosensitive resin composition using such a base generator and a lactone or cyclic siloxane as a base-reactive compound is photocured. Suitable for materials (UV adhesion, UV ink, UV adhesion, UV coating, etc.). Anionic polymerization with a guanidine represented by formula (IV) and a phosphazene derivative represented by formula (V) as a base-reactive compound applicable to the base generator of the third invention represented by formula (Z) Specific examples of possible lactone and cyclic siloxane structures are shown below (No. 6-1 to No. 6-4).

  It is preferable that content of the base generator in the photosensitive resin composition of this invention shall be 0.1-60 mass parts with respect to 100 mass parts of base reactive compounds. When the content of the base generator is less than 0.1 parts by mass, the base-reactive compound may not be allowed to react rapidly. On the other hand, when the content of the base generator exceeds 60 parts by mass, the base is generated. The presence of the agent may adversely affect the solubility of the base-reactive compound in the solvent, and the presence of an excessive amount of the base generator leads to high costs. The content of the base generator is preferably 1 to 60 parts by mass, more preferably 2 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the base-reactive compound. Is more preferable, and 2 to 15 parts by mass is particularly preferable. In the case of polymerizing lactones using the base generator according to the third invention represented by the formula (Z) as a base generator, it is preferable to coexist a small amount of alcohol such as ethanol, propanol, butanol, The base generator is preferably 0.1 to 0.5 parts by mass and the alcohol is preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the monomer (base-reactive compound).

  The photosensitive resin composition of the present invention has the above-described No. 1 as a base-reactive compound. 4-1. No. 4-12 and other epoxy compounds exhibiting polymerization reactivity (polymerizable epoxy compounds) 5-1 to No. It is preferable to use a silicon compound (polymerizable silicon compound) exhibiting polymerization reactivity such as 5-5. Such a photosensitive resin composition is polymerized by the action of light or heat to give a polymer. Especially, it is preferable to set it as the photosensitive resin composition containing the base reactive compound which starts a polymerization reaction with light.

  In order to form a pattern using such a photosensitive resin composition, for example, the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is applied to an appropriate solid surface such as a substrate. And then dried to form a coating film. And after performing pattern exposure with respect to the formed coating film and generating a base, it heat-processes on predetermined conditions, The polymerization reaction of the base reactive compound contained in the photosensitive resin composition is carried out. To encourage.

  Since the photosensitive resin composition of the present invention contains the base generator of the present invention, the polymerization reaction proceeds even at room temperature, but it is preferable to perform a heat treatment in order to allow the polymerization reaction to proceed efficiently. The conditions for the heat treatment may be appropriately determined depending on the exposure energy, the type of base generated from the base generator used, and the type of base-reactive compound such as an epoxy compound or silicon compound. It is preferable to be in the range of 150 ° C, and it is particularly preferable to be in the range of 60 ° C to 130 ° C. The heating time is preferably 10 seconds to 60 minutes, particularly preferably 60 seconds to 30 minutes. The pattern can be obtained by immersing this in a solvent that causes a difference in solubility between the exposed part and the unexposed part and developing.

  If necessary, the photosensitive resin composition of the present invention preferably contains a base proliferating agent that generates a base proliferatively by the action of a base. By including a base proliferating agent in the photosensitive resin composition of the present invention, the sensitivity of the resin composition can be further improved. In particular, when the light does not reach the deep part of the resin film (when the photosensitive layer is thick or contains a large amount of dye or pigment, etc.), the action of the photochemically generated base in the surface layer and the base by the base proliferating agent When the growth reaction is started, bases are generated thermochemically and in a chain manner, so that a base-catalyzed reaction in the deep part of the membrane can be expected. The base proliferating agent that can be used is not particularly limited, and examples thereof include JP-A No. 2000-330270 and JP-A No. 2002-128750. Arimitsu, M.M. Miyamoto and K.M. Ichimura, Angew. Chem. Int. Ed. , 39, 3425 (2000), and the like. The addition amount of the base proliferating agent may be appropriately determined depending on the base generator or base-reactive compound used, but is preferably in the range of 1 to 40% by mass with respect to the entire photosensitive resin composition. It is particularly preferable that the content be in the range of ˜20% by mass.

  In the photosensitive resin composition of the present invention, a sensitizer can be added in order to expand the photosensitive wavelength region and increase the sensitivity. The sensitizer that can be used is not particularly limited. For example, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene. , Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro -4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2 tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5 , 7-dimethoxycarbonylcoumarin) or coronene. These sensitizers may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the addition amount of the sensitizer may be appropriately determined depending on the base generator or base-reactive compound used, the required sensitivity, etc., but the entire photosensitive resin composition It is preferable that it is the range of 1-30 mass% with respect to. If the sensitizer is less than 1% by mass, the sensitivity may not be sufficiently increased. On the other hand, if the sensitizer exceeds 30% by mass, the sensitivity may be excessive. The addition amount of the sensitizer is particularly preferably in the range of 5 to 20% by mass with respect to the entire photosensitive resin composition.

  When the photosensitive resin composition of the present invention is applied to a predetermined substrate, a solvent may be appropriately contained as necessary. By including a solvent in the photosensitive resin composition, the coating ability can be increased, and workability is improved. The solvent is not particularly limited. For example, aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, Saturated or unsaturated hydrocarbon compounds such as isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, Di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibuty Ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl Ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o- Ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

  In the photosensitive resin composition of the present invention, the content of the solvent is, for example, uniformly applied when a photosensitive resin composition is applied on a predetermined substrate to form a layer of the photosensitive resin composition. The selection may be made as appropriate.

  In addition, you may make it add an additive suitably to the photosensitive resin composition of this invention in the range which does not inhibit the objective and effect of this invention. Examples of additives that can be used include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, Examples thereof include a plasticizer, a plastic accelerator, an anti-sagging agent, a curing accelerator, and a filler. One of these may be used alone, or two or more may be used in combination.

  The photosensitive resin composition of the present invention described above contains the base generator of the present invention and a base-reactive compound, so that the reaction between the base generated from the base generator and the epoxy compound proceeds in a chained manner. Thus, the photosensitive resin composition is excellent in curing speed and reaction efficiency, cured rapidly even at room temperature level, and sufficiently cured. The photosensitive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.

  The molded body applied as a photo-curing material can be used as a member in a field where characteristics such as heat resistance, dimensional stability, and insulation are effective, for example, paint or printing ink, color filter, film for flexible display, semiconductor, etc. Widely used as equipment, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members or building materials, printed materials, color filters, films for flexible displays, A semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, a building member, or the like is provided. In addition, the formed pattern has heat resistance and insulation, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, reflective It can be advantageously used as a protective film, other optical member or electronic member.

  The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and has the configuration of the present invention and can achieve the objects and effects. It goes without saying that modifications and improvements within the scope are included in the content of the present invention. Further, the specific structure, shape, and the like in carrying out the present invention are not problematic as other structures, shapes, and the like as long as the objects and effects of the present invention can be achieved. The present invention is not limited to the above-described embodiments, and modifications and improvements within the scope that can achieve the object of the present invention are included in the present invention.

  For example, in the above-described embodiment, the base generator of the present invention is exemplified by a compound obtained by adding one amidine or imidazole to the carboxylic acid represented by the formula (Y), but is not limited thereto. The base generator of the present invention includes those obtained by adding two carboxylic acids to amidines or imidazoles. As an example, a compound obtained by adding two carboxylic acids of the formula (Y) to diazabicycloundecene (DBU) is shown as the following formula (Y ′).

  In the above-described embodiment, as an example of the base generator of the present invention, No. 1-1'-No. 6-6 ′ compounds (carboxylates) were mentioned, but these are merely examples, and any combination of carboxylic acid and base having formula (X), formula (Y) or formula (Z) may be used. There is no particular limitation. No. 1-1'-No. 6-4 'shows an example in which alkali metal and alkaline earth metal cations are used as the metal M (cation) constituting the base generator of the present invention. 1-1'-No. Amidines represented by formula (I) or carboxylic acids disclosed in 6-4 ′ (excluding ketoprofen represented by No. 1-1 ′ to No. 1-4 ′) or represented by formula (II) In combination with imidazoles to be prepared, or 1-1'-No. A guanidine represented by the formula (IV) or a phosphazene derivative represented by the formula (V) may be combined with the carboxylic acid disclosed in 6-4 'as the base generator of the present invention.

In the above-described embodiment, as an example of the base-reactive compound constituting the photosensitive resin composition of the present invention, No. 2-1. Although the compound of 5-5 was mentioned, the base reactive compound which can be used is not limited to these, Arbitrary compounds which react by the effect | action of a base and harden | cure by bridge | crosslinking etc. can be used.
In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this Example at all.

[Example 1]
Production of base generator (1):
To a solution obtained by dissolving 5.0 g (20 mmol) of ketoprofen represented by the formula (III) in 15 mL of methanol, a solution obtained by dissolving 1.4 g (20 mmol) of sodium ethoxide (C ₂ H ₅ ONa) in 25 mL of methanol was dropped. The reaction was allowed to proceed for 1 hour at room temperature. After completion of the reaction, the solvent was distilled off, and reprecipitation was performed twice using chloroform as a good solvent and diethyl ether as a poor solvent, whereby the base generator of the present invention represented by the formula (No. 1-1 ′) was obtained. Was obtained in 38% yield.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.25 (3H, d, J = 7.2 Hz, CH ₃ ), 3.4 (1H, d, J = 7.2 Hz, CH), 7.08-7.66 (9H, m, ArH)
Decomposition point (° C): 156 ° C (DSC)

Confirmation of alkali generation ability by light irradiation (1):
After dropping a suitable amount of the base generator obtained in Example 1 onto a pH test paper (Whatman indicator paper pH 1-11) together with water (yellow, which is the color of the test paper: pH is 5 to 6), When light having a wavelength of 254 nm was irradiated from above, the color changed to dark green, and the pH was about 11. From the above, it was confirmed that the base generator obtained in Example 1 generated alkali upon irradiation with light and functioned as a base.

Confirmation of photolysis behavior:
For the base generator obtained in Example 1, methanol was used as a solvent, and the photodegradation behavior was confirmed using the following measurement method.

(Measuring method)
A methanol solution (3 × 10 ⁻⁵ mol / L) of the base generator of Example 1 was irradiated with light having a wavelength of 254 nm or 313 nm, and an ultraviolet-visible spectrophotometer (MultiSpec-1500 / manufactured by Shimadzu Corporation) was used. The change of the UV spectrum with time was confirmed. The results are shown in FIG. 1 (wavelength: 254 nm) and FIG. 2 (wavelength: 313 nm).

  As shown in FIGS. 1 and 2, the base generator of the present invention obtained in Example 1 shows that the absorption intensity near 237 nm increases with the exposure dose of light irradiation, and photodecomposition is observed. The behavior could be confirmed.

[Example 2]
Production of photosensitive resin composition (1):
The alkali generator obtained in Example 1 with respect to 0.1 g (100 parts by mass) of polyglycidyl methacrylate (PGMA, M _W = 10000), which is an epoxy compound represented by the formula (No. 4-12) Was contained in an amount of 0.0078 g (8 parts by mass) (4.0 mol% with respect to the monomer unit of PGMA) to obtain a photosensitive resin composition of the present invention.

[Test Example 1]
Confirmation of photoinsolubilization behavior (1) (temperature dependence):
The photosensitive resin composition obtained in Example 2 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 1 minute to produce a film having a thickness of 1.3 μm. This film was irradiated with monochromatic light of 254 nm, postbaked at 120 ° C. for 5 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. Then, the same operation was carried out by changing the post-baking temperature to 140 ° C. and 160 ° C., and the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was created for each. The obtained sensitivity curve is shown in FIG.

  As the photosensitive resin composition of the present invention is irradiated with light, the crosslinking reaction of the epoxy compound (PGMA) proceeds and becomes insoluble in chloroform. FIG. 3 is a graph showing the temperature dependence of the relationship between the exposure dose and the remaining film ratio. As shown in FIG. 3, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) occurred with higher efficiency as the heating temperature was higher.

[Test Example 2]
Confirmation of photoinsolubilization behavior (2) (time dependence):
The photosensitive resin composition obtained in Example 2 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 1 minute to produce a film having a thickness of 1.3 μm. This film was irradiated with monochromatic light of 254 nm, postbaked at 140 ° C. for 5 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. Then, the same operation was performed with the post-baking time changed to 10 minutes and 20 minutes, and the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was created for each. The obtained sensitivity curve is shown in FIG.

  FIG. 4 is a diagram showing the heating time dependency of the relationship between the exposure amount and the remaining film ratio. As shown in FIG. 4, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating time was increased.

[Example 3]
Production of photosensitive resin composition (2):
Example 2 is the same as Example 2 except that 0.0037 g (4 parts by mass) (2.0 mol% with respect to the monomer unit of PGMA) of the base generator obtained in Example 1 is contained. The photosensitive resin composition of the present invention was obtained using various methods.

[Example 4]
Production of photosensitive resin composition (3):
Example 2 was the same as Example 2 except that 0.012 g (12 parts by mass) of the base generator obtained in Example 1 (6.0 mol% with respect to the monomer unit of PGMA) was contained. The photosensitive resin composition of the present invention was obtained using various methods.

[Test Example 3]
Confirmation of photoinsolubilization behavior (3) (concentration dependence):
The photosensitive resin composition obtained in Example 2 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 1 minute to produce a film having a thickness of 1.3 μm. This film was irradiated with monochromatic light of 254 nm, postbaked at 120 ° C. for 5 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. And the same operation was implemented with respect to the photosensitive resin composition obtained in Example 3 and Example 4, and the relationship (sensitivity curve) of the exposure amount and the remaining film rate was created about each. The obtained sensitivity curve is shown in FIG.

  FIG. 5 is a graph showing the concentration dependency of the relationship between the exposure amount and the remaining film ratio. As shown in FIG. 5, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the concentration of the base generator of the present invention was increased (added amount was increased).

[Test Example 4]
Confirmation of base generation ability by light irradiation (2):
Tetraethoxysilane (TEOS) 0.50 g, the base generator 0.066 g obtained in Example 1 and water 0.086 g were dissolved in ethanol 0.22 g and transferred to a vial tube as a sample solution. This sample solution was irradiated with ultraviolet light from a Hg—Xe lamp, and the amount of SiO ₂ produced as the TEOS sol-gel reaction progressed was measured. FIG. 6 shows the relationship between the exposure time and the amount of SiO ₂ produced.

As shown in FIG. 6, it can be seen that when the sample solution is irradiated with ultraviolet light, the amount of SiO ₂ produced increases with the exposure time. This indicates that alkali was generated from the base generator of the present invention in the sample solution by light irradiation, and the sol-gel reaction of tetraethoxysilane (TEOS) proceeded. From the above, it was confirmed that the base generator of the present invention generated a base according to the exposure time.

[Example 5]
Production of base generator (2):
After dropwise addition of a tetrahydrofuran (THF) solution of 1.1 g (7.9 mmol) of TBD shown in formula (IV-c) to a solution of ketoprofen 2.0 g (7.9 mmol) shown in formula (III) in tetrahydrofuran (THF). And allowed to react at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off, ether was added and stirred, followed by decantation to remove unreacted ketoprofen and TBD. After the removal, drying under reduced pressure was performed to obtain a colorless viscous liquid of the base generator of the present invention represented by the formula (IV) in a yield of 58%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.50 (3H, d, J = 6.9 Hz, CHCH ₃ ) 1.88-1.96 (H, m, CH ₂ ), 3. _{18-3.26 (8H, m, CH 2} ), 3.70 (1H, q, J = 6.9Hz, CHCH 3), 7.30-7.85 (9H, m, Ph-H), 10 .80 (2H, br, NH)

[Example 6]
Production of photosensitive resin composition (4):
The base generator obtained in Example 5 was added to 0.1 g (100 parts by mass) of polyglycidyl methacrylate (PGMA, Mw = 10000), which is an epoxy compound represented by the formula (No. 4-12). .0014 g (1.4 parts by mass) (0.5 mol% with respect to the monomer unit of PGMA) was contained to obtain the photosensitive resin composition of the present invention.

[Example 7]
Production of photosensitive resin composition (5):
Example 6 is the same as Example 6 except that 0.0028 g (2.8 parts by mass) (1.0 mol% with respect to the monomer unit of PGMA) of the base generator obtained in Example 5 is contained. The photosensitive resin composition of this invention was obtained using the method similar to.

[Example 8]
Production of photosensitive resin composition (6):
Example 6 In Example 6, except that 0.0055 g (5.5 parts by mass) (2.0 mol% based on the monomer unit of PGMA) of the base generator obtained in Example 5 was contained. The photosensitive resin composition of this invention was obtained using the method similar to.

[Test Example 5]
Confirmation of photoinsolubilization behavior (concentration dependence)
The photosensitive resin composition obtained in Example 6 was dissolved in 1.0 g of chloroform. This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 30 seconds to produce a film having a thickness of 1.0 μm. This film was irradiated with monochromatic light of 254 nm, post-baked at a temperature of 100 ° C. for 5 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. And the same operation was implemented with respect to the photosensitive resin composition obtained in Example 7 and Example 8, and the relationship (sensitivity curve) of the exposure amount and the remaining film rate was created about each. The obtained sensitivity curve is shown in FIG.

  FIG. 7 is a graph showing the concentration dependency of the relationship between the exposure amount and the remaining film ratio. As shown in FIG. 7, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the concentration of the base generator of the present invention was increased (added amount was increased).

  The present invention can be advantageously used as a photosensitive resin material that provides a highly sensitive photocuring material, resist material (pattern forming material), and the like.

Claims (6)

A base generator characterized by being a carboxylate salt composed of a carboxylic acid and an alkali metal or an alkaline earth metal and represented by the following formula (X).

(In the formula (X), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ each represent a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, M represents an alkali metal or an alkaline earth metal, and n represents an integer of 1 or 2. ) A base generator, which is a carboxylic acid salt composed of a carboxylic acid (excluding ketoprofen) and a base and represented by the following formula (Y).

(In the formula (Y), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, Q is an amidine represented by the following formula (I), and a formula (II). Bases consisting of any of the following imidazoles):

(In formula (I), n represents an integer of 1 to 3)

(In formula (II), each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (which may contain a heteroatom such as S), or a phenyl group.) A base generator characterized by being a carboxylate salt comprising a carboxylic acid and a base and represented by the following formula (Z).

(In the formula (Z), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, G is a guanidine represented by the following formula (IV), and a formula (V). A phosphazene derivative, a base consisting of any one of

(In formula (IV), R _{1 to} R ₅ each independently represents a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

(In formula (V), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)   The base generator according to claim 1 or 3, wherein the carboxylic acid is ketoprofen.   A photosensitive resin composition comprising the base generator according to any one of claims 1 to 4 and a base-reactive compound.   6. The photosensitive resin composition according to claim 5, wherein the base-reactive compound is an epoxy compound and / or a silicon compound.

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