JP2012250969A - Carboxylic acid compound, base generator, and photosensitive resin composition containing the base generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carboxylic acid compound which has excellent reaction efficiency without generating carbon dioxide when generating a base, a base generator and a photosensitive resin composition containing the base generator.SOLUTION: The carboxylic acid compound acts as the base generator for which carboxylic acid causes photocyclization reaction by light irradiation to generate the base, and when it is applied to a base reactive compound such as an epoxy compound, since a base generating reaction is sequentially generated, the reaction efficiency is excellent, and carbon dioxide is not generated when generating the base. Also, the photosensitive resin composition can provide a cured film of high product characteristics and product values without generating irregularities on the cured film by bubbles of the carbon dioxide. The photosensitive resin composition which demonstrates such an effect is suitably usable for a highly sensitive photo curing material or a resist material or the like for instance.

Description

  The present invention relates to a carboxylic acid compound, a base generator, and a photosensitive resin composition containing the base generator. More specifically, the present invention relates to a carboxylic acid compound that generates a base by active energy rays such as light, a base generator, 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 for curing by treatment are provided (see, for example, Patent Document 1 and Patent Document 2).
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JP 2005-264156 A Japanese Patent Laid-Open No. 2007-10185

However, the methods that have been provided conventionally have problems such as the fact that the reaction of generating a base by the action of light is not performed rapidly, and thus the practicality is poor, and improvement has been demanded. In addition, the conventional base generator is accompanied by the generation of carbon dioxide (CO ₂ ) as a decomposition product when generating the base. Such carbon dioxide is present when the photosensitive resin composition is formed into a film. In some cases, bubbles were formed, causing unevenness in the cured film. Here, in the case where the photosensitive resin composition is formed, if bubbles remain in the cured film, the strength of the cured film is reduced, and when used as an adhesive, the adhesive strength is reduced. In the case of using it as a stopping material or a coating material, there arises a problem that the barrier property against impurities in the air such as water and basic substances is lowered, which is not preferable.

  The present invention has been made in view of the above-mentioned problems. For example, the present invention can be used for a crosslinking reaction of an epoxy compound. When applied to an epoxy compound, the base generation reaction is performed in a chain manner. Therefore, the present invention provides a carboxylic acid compound, a base generator, and a photosensitive resin composition containing the base generator, which have good reaction efficiency and no generation of carbon dioxide when a base is generated.

  In order to solve the above problems, the carboxylic acid compound according to the present invention is a carboxylic acid compound composed of a carboxylic acid and a base, and is represented by the following formula (X).

（式（Ｘ）中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ、独立して水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、シアノ基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、または有機基を示し、同一であっても異なっていてもよい。Ｒ_１、Ｒ_２、Ｒ_３は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７はそれぞれ、独立して水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アルコキシ基、アミド基または有機基を示し、同一であっても異なっていてもよい。Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子を含んでいてもよい。また、Ｂは塩基としてはたらく塩基類、を示す。）

(In formula (X), R ₁ , R ₂ and R ₃ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group. , Sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or an organic group, which may be the same or different, and R ₁ , R ₂ , and R ₃ are two of them. The above may combine to form a cyclic structure, and may include a heteroatom bond, and R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, halogen, hydroxyl group, mercapto Group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, a Amino group, an alkoxy group, an amido group or an organic group, which may be different even in the same _{.R 4, R 5, R 6} , R 7 are those two or more ring structure by bonding with It may be formed and may contain a heteroatom, and B represents a base that serves as a base.)

  In the present invention described above, the carboxylic acid compound according to the present invention is characterized by comprising the following formula (X ′).

（式（Ｘ’）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_６は前記式（Ｘ）に示した基と同じであり、また、Ｒ_１、Ｒ_２は、結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ_４、Ｒ_５、Ｒ_６は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子を含んでいてもよい。また、ｎは０〜６の整数を示す。）

(In the formula (X ′), R ₁ , R _2, R ₄ , R ₅ and R ₆ are the same as the group shown in the formula (X), and R ₁ and R ₂ are bonded to form a cyclic group. A structure may be formed, and a bond of a hetero atom may be included, and two or more of R ₄ , R ₅ , and R ₆ may be bonded to form a cyclic structure. (It may contain an atom, and n represents an integer of 0 to 6.)

  The base generator according to the present invention comprises the carboxylic acid compound according to the present invention described above.

  The base generator according to the present invention is selected from the group consisting of compounds represented by the following formula (I), formula (II), formula (IV) and formula (V) in the present invention. It is at least one kind.

（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.)

（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 photosensitive resin composition according to the present invention includes the above-described base generator according to the present invention and a base-reactive compound.

  The photosensitive resin composition according to the present invention is characterized in that, in the above-described present invention, the base-reactive compound is at least one selected from the group consisting of an epoxy compound, a silicon compound, and an oxetane compound. .

  The photosensitive resin composition according to the present invention further includes a thiol compound in the above-described present invention.

  The carboxylic acid compound according to the present invention is a carboxylic acid compound that undergoes a photocyclization reaction by light irradiation to generate a base, and no carbon dioxide gas is generated when the base is generated.

  In addition, the base generator according to the present invention comprising such a carboxylic acid compound, when applied to a base-reactive compound such as an epoxy compound, has a good reaction efficiency because a base-generating reaction is carried out in a chain. Since the carboxylic acid undergoes a photocyclization reaction upon irradiation with light to generate a base, it acts as a base generator that does not generate carbon dioxide when the base is generated.

  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 proceeds in a chain manner. In order to provide excellent reaction efficiency, curing is sufficiently performed. In addition, since the added base generator is not accompanied by the generation of carbon dioxide when the base is generated, a cured film having high product characteristics and product value is provided without causing unevenness due to bubbles of carbon dioxide in the cured film. be able to.

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: 254 nm) of the base generator obtained in Example 2. It is the figure which showed the photodegradation behavior (wavelength: 254 nm) of the base generator obtained in Example 3. It is the figure which showed the photodegradation behavior (wavelength: 254 nm) of the base generator obtained in Example 4. It is the figure which compared the photodegradation behavior of the base generator obtained in Example 1 and Example 4. FIG. 3 is a diagram showing changes in UV spectrum of the base generator obtained in Example 1. 1 is a diagram showing a ¹ H-NMR spectrum of a base generator obtained in Example 1. FIG. It is the figure which showed the relationship between the exposure amount in 1720cm < ^-1 >, and the increase rate of peak area ratio. It is the figure which showed the relationship between the exposure amount in 1374cm < ^-1 >, and the decreasing rate of peak area ratio. It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate) of the photosensitive resin composition obtained in Example 5. It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate) of the photosensitive resin composition obtained in Example 6. It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate) of the photosensitive resin composition obtained in Example 7. It is the figure which compared the sensitivity evaluation result of the photosensitive resin composition obtained in Example 6-1 and Example 7-1. It is the figure which showed the relationship between the heating time in 907cm < ^-1 >, and the decreasing rate of peak area ratio. It is the figure which showed the photodegradation behavior (wavelength: 254 nm) of the base generator obtained in Example 8. It is the figure which showed the photodegradation behavior (wavelength: 313 nm) of the base generator obtained in Example 8. It is the figure which showed the relationship between exposure amount and peak intensity. In Experiment 12, it is the figure which showed the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 9. FIG. In Experiment 12, it is the figure which showed the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 10. FIG. In Experiment 12, it is the figure which showed the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 11. FIG. In Experiment 13, it is the figure which showed the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 9. FIG. In Experiment 13, it is the figure which showed the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 10. FIG. In Experiment 13, it is the figure which showed the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 11. FIG. In Experiment 13, it is the figure which compared the result of the pencil hardness measurement of the photosensitive resin composition obtained in Example 9 thru | or Example 11.

  Hereinafter, one embodiment of the present invention will be described. The carboxylic acid compound according to the present invention is a carboxylic acid salt represented by the following formula (X) and comprising a carboxylic acid represented by the formula (III) and a base B serving as a base.

For the carboxylic acid compound represented by the formula (X) (carboxylate represented by the formula (III)), R ₁ , R ₂ and R ₃ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide. Group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group. It may be. Two or more of R ₁ , R ₂ , and R ₃ may be bonded to form a cyclic structure, and may include a hetero atom bond. R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group. Group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, alkoxy group, amide group or organic group, which may be the same or different. Two or more of R ₄ , R ₅ , R ₆ and R ₇ may be bonded to form a cyclic structure, and may contain a hetero atom. B represents a base that acts as a base.

  In addition, the following aromatic ring in the carboxylic acid constituting the formula (X) or the formula (III) may be a polycyclic aromatic ring such as naphthalene, anthracene, or pyrene other than the benzene ring, and the aromatic ring in the aromatic ring may be It may be a heterocyclic aromatic ring containing a hetero atom.

  Such a carboxylic acid compound uses an alkali such as an alkali metal or an alkaline earth metal or a base such as a base compound as a binding target with the carboxylic acid, and the carboxylic acid undergoes a photocyclization reaction upon irradiation with light, and the base B It will work as a base generator that generates water.

(Scheme 1)

In addition, as shown in Scheme 1, such a carboxylic acid compound generates a base by photocyclization reaction of carboxylic acid by light irradiation, and thus generates carbon dioxide (CO ₂ ) as a decomposition product when generating the base. There is nothing. Such carbon dioxide gas becomes bubbles when the photosensitive resin composition is formed, and the cured film has irregularities, and the strength of the cured film is lowered. When the carboxylic acid compound according to the present invention was applied to a base-reactive compound such as an epoxy compound as a base generator, the reaction efficiency was good and at the time of base generation. A cured film excellent in product characteristics and product value without generation of carbon dioxide can be provided.

The carboxylic acid compound according to the present invention is a carboxylic acid compound represented by the following formula (X ′) (as shown in the following formula (III ′), a cyclic structure is formed by R ₃ and R ₇ in the formula (III). The olefin part of the carboxylate before photocyclization is fixed without free rotation, and photocyclization is likely to occur. Therefore, when used as a base generator, a relatively small exposure amount Provides a base generator with good sensitivity. In addition, the photosensitive resin composition containing such a sensitive base generator is cured at a relatively short exposure time (about 1 to 2 minutes) or at a low post-heating temperature (room temperature to about 50 ° C.). A light-curing material. In the formula (X ′) and the formula (III ′), R ₁ , R _2, R ₄ , R ₅ , R ₆ are the same as the groups shown in the above formula (X), and R ₁ , R ₂ may be bonded to form a cyclic structure and may contain a hetero atom bond. Two or more of R ₄ , R ₅ and R ₆ may be bonded to each other to form a cyclic structure, and may contain a hetero atom. N represents an integer of 0 to 6, and n is preferably 1 to 3.

  Specific examples of the carboxylic acid represented by the formula (III) that is a carboxylic acid constituting the carboxylic acid compound include formulas (III-1), (III-2), and formulas (III ′) corresponding to the formula (III ′). -3).

  In order to synthesize the carboxylic acid represented by the formula (III), for example, the following may be performed. The carboxylic acid of the formula (III-1) can be obtained by converting phthalaldehyde acid to methyl ester, converting the aldehyde group to olefin by Wittig reaction, and then hydrolyzing the methyl ester. The carboxylic acid of the formula (III-2) can be obtained by converting methyl 2-formyl-3,5-dimethoxybenzoate into olefin by wittig reaction and hydrolyzing the methyl ester. The carboxylic acid of the formula (III-3) is obtained through bromination of 7-methoxy-1-tetralone, conversion of a carbonyl group into an olefin by Wittig reaction, and Grignard reaction. Other carboxylic acids may be synthesized according to the synthesis methods shown in the above formulas (III-1) to (III-3).

  Among the bases B constituting the carboxylic acid compound represented by the formula (X), examples of the alkali include alkali metals and alkaline earth metals. Among these, examples of the alkali metal include sodium (Na) and potassium (K), and examples of the alkaline earth metal include calcium (Ca) and barium (Ba).

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

  As the bases B, for example, amines, compounds containing pyridyl groups, hydrazine compounds, amide compounds, quaternary ammonium hydroxide salts, mercapto compounds, sulfide compounds, phosphine compounds and the like can be used. Is preferably used. As the amine, primary amine, secondary amine, and tertiary amine can be used.

Examples of the primary amine include methylamine, ethylamine, n-propylamine, n-butylamine, amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine, isopropylamine, isobutylamine, sec-butylamine, tert- Butylamine, 1-methylbutylamine, 1-ethylpropylamine, isoamylamine, 1,2-dimethylpropylamine, tert-amylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminohexane Tan, 1-methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, tert-octylamine, ethyldiamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1 , 2-diamino-2-methylpropane, 1,5-diaminopentane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, 1,7-diaminoheptane, 1,8-diaminooctane, , 9-Diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 2-butyl-2-ethyl-1,5-pentanediamine, cyclopropylamine, (aminomethyl) cyclopropane, cyclobutylamine, cyclopentylamine 5-amino-2,2,4-trimethyl-1-cyclopenta Methylamine, cyclohexylamine, 2-methylhexylamine, 4-methylcyclohexylamine, 4,4'-methylenebis (cyclohexylamine), 2,3-dimethylcyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine) 1,2-diaminocyclohexane, cyclohexanemethylamine, 1,8-diamino-p-menthane, 5-amino-1,3,3-trimethylcyclohexanemethylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, 2 -Aminonorbornene, bornylamine, miltanylamine, 1-adamantanamine, 1-adamantanemethylamine, allylamine, oleylamine, zeranylamine, 2,2,2-trifluoromethylamine, 2-methoxyethyl Ruamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-butoxypropylamine, 2-amino-1-methoxypropane, 3-isopropoxypropylamine, 2,2′-oxybis (ethyleneamine), 2,2 '-(Ethylenedioxy) bis (ethylamine), 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 3-amino-1-propanol vinyl ether, Tetrahydrofurfurylamine, 2,5-dihydro-2,5-dimethoxyfurfurylamine, aminoacetaldehyde dimethyl acetal, 4-aminobutyraldehyde diethyl acetal, ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-p Lopanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2- Amino-3-methyl-1-butanol, 6-amino-1-hexanol, 2-amino-1-hexanol, 1-amino-1-cyclopentanemethanol, 2-aminocyclohexanol, 4-aminocyclohexanol, 1- Aminomethyl-1-cyclohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexane, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (Propylamino) ethanol, 2- (tert-butylamino) ethanol, 3-amino-1,2 Propanediol, SERINOL, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, BIS-HOMOTORIS, 1,3 -Diamino-2-hydroxypropane, 1-amino-deoxysorbitol, 2-aminomethyl-15-crown-5, 2-aminomethyl-18-crown-6, aniline, orthotoluidine, metatoluidine, paratoluidine, 2- Ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-butylaniline, 3- Butylaniline, 4-bu Ruaniline, 2-sec-butylaniline, 3-sec-butylaniline, 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 4-pentylaniline, 4 -Hexylaniline, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-cyclohexylaniline, 2,2'-ethylene Dianiline, orthoanisidine, metaanisidine, paraanisidine, orthophenetidine, metaphenetidine, paraphenetidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothio Enol, 2-aminobenzyl alcohol, 2-aminophenylethyl alcohol, 3-aminophenylethyl alcohol, 4-aminophenylethyl alcohol, 3- (1-hydroxyethyl) aniline, 2- (methylmercapto) aniline, 3- ( Methylmercapto) aniline, 4- (methylmercapto) aniline, 2-aminophenyl disulfide, 2-isopropenylaniline, 4,4′-ethylenedianiline, 3,3′-methylenedianiline, 4,4′-methylenedi Aniline, 4,4′-methylenebis (3-chloro-2,6-diethylaniline), 4,4′-diaminostilbene, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4,4 ′ -Oxydianiline, 4,4'-thiodianiline, 4 ", 4"" (Hexafluoroisopropylidene) -bis- (4-phenylaniline), oxydianiline, 4-aminophenyl sulfide, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6 -Dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 6-ethylorthotoluidine, 2,6-diethylaniline, 2-isopropyl-6-methylaniline, 2,6-diisopropylaniline, 1-amino -5,6,7,8-tetrahydronaphthalene, 5-aminoindane, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromo Aniline, 3-bromoaniline, 4-bromoaniline, 2-iodo Niline, 3-iodoaniline, 4-iodoaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 3- (trifluoromethoxy) aniline, 4- (Trifluoromethoxy) aniline, 3- (1,1,2,2-tetrafluoroethyl) aniline, 3-fluoro-2-methylaniline, 3-chloro-2-methylaniline, 2-chloro-6-methylaniline 2,6-difluoroaniline, 2,3-difluoroaniline, 2,6-dichloroaniline, 2,3-dichloroaniline, 2,6-dibromoaniline, 2-methoxy-6-methylaniline, 3-fluoroorthoaniline Cidin, 3-amino-2-methylbenzyl alcohol, 2-amino-3-methylbenzyl alcohol, -Aminometacresol, 2,3-diaminophenol, orthotoluidine, 4,4'-ethylenedimetatoluidine, 2,5-di-tert-butylaniline, 3-fluoro-4-methylaniline, 2-fluoro-4 -Methylaniline, 5-fluoro-2-methylaniline, 2-fluoro-5-methylaniline, 4-fluoro-2-methylaniline, 2-fluoro-6-methylaniline, 2,5-bis (trifluoromethyl) Aniline, 2-fluoro-6- (trifluoromethyl) aniline, 2-fluoro-3- (trifluoromethyl) aniline, 2,4-difluoroaniline, 3,4-difluoroaniline, 2,5-difluoroaniline, 3 -Chloro-4-fluoroaniline, 2-chloro-4-fluoroaniline, 2-bromo-4-fluoro Aniline, 4-bromo-2-fluoroaniline, 2-bromo-4-iodoaniline, 2-chloro-4-aminotoluene, 2-chloro-4-methylaniline, 2-chloro-5-methylaniline, 5-chloro 2-methylaniline, 4-chloro-2-methylaniline, 3,4-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 4-bromo-2-methylaniline, 4-bromo-3 -Methylaniline, 3-bromo-4-methylaniline, 2-bromo-4-methylaniline, 4-bromo-2-chloroaniline, 2,4-dibromoaniline, 2,5-dibromoaniline, 4-fluoro-2 -(Trifluoromethyl) aniline, 4-fluoro-3- (trifluoromethyl) aniline, 2-fluoro-5- (trifluoromethyl) Aniline, 4-chloro-3- (trifluoromethyl) aniline, 4-chloro-2- (trifluoromethyl) aniline, 4-bromo-2- (trifluoromethyl) aniline, 4-bromo-3- (trifluoro Methyl) aniline, 2-bromo-5- (trifluoromethyl) aniline, 2-chloro-5- (trifluoromethyl) aniline, 5,5 ′-(hexafluoroisopropylidene) diortoluidine, 4-methoxy-2 -Methylaniline, 2-methoxy-5-methylaniline, 5-methoxy-2-methylaniline, 5-tert-butyl orthoanisidine, 2-methoxy-5- (trifluoromethyl) aniline, 6-chlorometaanisidine , 4-aminoveratrol, 3,4- (methylenedioxy) aniline, 1,4-benzodioxane 6-amine, 4′-aminobenzo-15-crown-5, 2,4-dimethoxyaniline, 4-aminocresol, 2,5-dimethoxyaniline, 5-amino-2-methoxyphenol, 3-aminoorthocresol, 2 -Aminoorthocresol, 2-amino-tert-butylphenol, 2-amino-tert-amylphenol, 6-aminometacresol, 4-aminometacresol, 2-amino-5-methylbenzyl alcohol, 3-amino-4- Methylbenzyl alcohol, 2-amino-4-chlorophenol, 4-amino-3-chlorophenol, 2-amino-5-chlorobenzyl alcohol, 5-chloroorthoanisidine, 3-fluoroloparaanisidine, 3-chloro Paraanisidine, 2-amino-4- (trifluoromethyl) ) Benzenethiol, 3,5-dimethylaniline, 3,5-ditert-butylaniline, 3,5-bis (trifluoromethyl) aniline, 3,5-difluoroloaniline, 3,5-dichloroaniline, 3, 5-dimethoxyaniline, 3-methoxy-5- (trifluoromethyl) aniline, 2,4,6-trimethylaniline, 4,4′-methylenebis (2,6-dimethylaniline), 4,4′-methylenebis (2 , 6-diethylaniline), 4,4′-methylenebis (2,6-diisopropylaniline), 2,4,6-tri-tert-butylaniline, 2-chloro-4,6-dimethylaniline, 2,6- Dichloro-3-methylaniline, 3-chloro-2,4-difluoroaniline, 2,3,4-trichloroaniline, 2,3,4-trifluoro Aniline, 2,3,6-trifluoroaniline, 2,4,6-trifluoroaniline, 2,6-dibromo-4-methylaniline, 3-chloro-2,6-diethylaniline, 4-bromo-2, 6-dimethylaniline, 4-bromo-2
, 6-difluoroaniline, 2-chloro-3,5-difluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2,4-dibromo-6-fluoroaniline, 2,6-dibromo-4-fluoro Aniline, 2,6-dichloro-4- (trifluoromethyl) aniline, 4-chloro-2,6-dibromoaniline, 4-amino-2,6-dichlorophenol, 3,4,5-trichloroaniline, 3, 4,5-trimethoxyaniline, 3,3 ′, 5,5′-tetramethylbenzidine, 2-bromo-4,6-difluoroaniline, 2,4,6-trichloroaniline, 2,6-dichloro-4- (Trifluoromethoxy) aniline, 2-bromo-3,5-bis (trifluoromethyl) aniline, 2,4,6-tribromoaniline, 2-chloro-4-fur Oro-5-methylaniline, 2,4,5-trifluoroaniline, 2,4,5-trichloroaniline, 4-chloro-2-methoxy-5-methylaniline, 4-amino-2,5-dimethylphenol, 4-amino-2,6-dibromophenol, 3,5-dichloro-2,6-diethylaniline, 2,3,5,6-tetrachloroaniline, 2,3,5,6-tetrafluoroaniline, 2, 3,4,5-tetrafluoroaniline, 2,3,4,6-tetrafluoroaniline, 2-bromo-3,4,6-trifluoroaniline, 2-bromo-4,5,6-trifluoroaniline, 2-amino-2,4-dichloro-3-methylphenol, 2,3,5,6-tetrafluoro-4-trifluoromethylaniline, 2,3,4,5,6-pentafluoroaniline Phosphorus, 4,4'-diaminooctafluorobiphenyl, 4-methoxy-3-biphenylamine, 4-bromo-2,3,5,6-tetrafluoroaniline, 1,2-phenylenediamine, 2,3-diaminotoluene 3,4-diaminotoluene, 3,3′-diaminobenzidine, 4-chloro-1,2-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine 1,2,4,5-benzenetetramine, 4,5-dichloro-1,2-phenylenediamine, 1,3-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminotoluene, 2,4, 6-trimethyl-1,3-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 2,4-diaminophenol, 4- (2 Hydroxyethylthio) -1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-diaminotoluene, 2,5-dimethyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2-aminobiphenyl, 4-amino Biphenyl, 2,4,6-triphenylaniline, 2-amino-4-phenylphenol, 5-phenylorthoanisidine, benzylamine, α-methylbenzylamine, aminodiphenylmethane, tritylamine, 1,2-diphenylethylamine, 2,2-diphenylethyleneamine, 2-amino-1,2-diphenylethano Phenethylamine, 2-amino-3-phenyl-1-propanol, 2-phenylcyclopropylamine, 3-phenyl-1-propylamine, 3,3-diphenylpropylamine, 1-methyl-3-phenylpropylamine, 4 -Phenylbutylamine, 1,2-diphenylethylenediamine, 1,2-bis (4-methoxyphenyl) ethylenediamine, 4- (2,4-di-tert-amylphenoxy) butylamine, 2-amino-1-phenylethanol, 2 -Phenylglycinol, 2-amino-3-phenyl-1-propanol, NORPHEDRINE, 2-methylbenzylamine, 1-aminoindane, 2-aminoindane, 1,2,3,4-tetrahydro-1-naphthylamine, 2 -(Trifluoromethyl) benzyl Amine, 2-fluorobenzylamine, 2-fluorophenethylamine, 2-chlorobenzylamine, 2-chlorophenethylamine, 2-bromobenzylamine, 2-methoxybenzylamine, 2-methoxyphenethylamine, 2-ethoxybenzylamine, 2- [ 2- (aminomethyl) phenylthio] benzyl alcohol, 2-aminobenzylamine, 3-methylbenzylamine, 3- (trifluoromethyl) benzylamine, metaxylenediamine, 3-fluorobenzylamine, 3-fluorophenethylamine, 3- Chlorobenzylamine, 3-chlorophenethylamine, 3-bromobenzylamine, 3-iodobenzylamine, 3-methoxyphenethylamine, 4-methylbenzylamine, paraxylenediamine, 4- (trifluoro (Romethyl) benzylamine, α, 4-dimethylbenzylamine, 2- (paratoluyl) ethylamine, 4-fluorobenzylamine, 4-fluorophenethylamine, 4-chlorobenzylamine, 4-bromobenzylamine, 4-bromophenethylamine, 4- Fluoro-α-methylbenzylamine, 4-fluorophenethylamine, 4-chlorophenethylamine, 4-methoxybenzylamine, 4-methoxyphenethylamine, 4- (trifluoromethoxy) benzylamine, 4-aminobenzylamine, 2- (4- Aminophenyl) ethylamine, TYRAMINE, 3,5-bis (trifluoromethyl) benzylamine, 3-fluoro-5- (trifluoromethyl) benzylamine, 2,6-difluorobenzylamine, 2,4-diflu Orobenzylamine, 2,5-difluorobenzylamine, 3,4-difluorobenzylamine, 2,4-dichlorobenzylamine, 3,4-dichlorobenzylamine, 2,4-dichlorophenethylamine, 2,3-dimethoxybenzylamine 3,5-dimethoxybenzylamine, 2,4-dimethoxybenzylamine, 3,4-dimethoxybenzylamine, 2,5-dimethoxyphenethylamine, 3,4-dimethoxyphenethylamine, piperonylamine, 3,4,5-trimethoxybenzyl Amine, 2,4,6-trimethoxybenzylamine, 1-aminoindanol, 1-naphthalenemethylamine, 1- (1-naphthyl) ethylamine, 9-aminofluorene, 1-pyrenemethylamine, α, ω-diamino Polyethylene glycol, α, - diamino polypropylene glycol, alpha, .omega.-diamino polydimethylsiloxane or polyallyl amine.

  Examples of the secondary amine include dimethylamine, N-ethylmethylamine, diethylamine, N-methylpropylamine, N-methylisopropylamine, N-ethylisopropylamine, dipropylamine, diisopropylamine, N-methylbutylamine, N-ethylbutylamine, N-methyl-tert-butylamine, N-tert-butylisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, tert-amyl-tert-butylamine, dipentylamine, N-methylhexylamine, Dihexylamine, tert-amyl-tert-octylamine, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N-methyloctadecylamine, N, N'-dimethylethyl Diamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3-propanediamine, N, N′-diethyl-1,3-propanediamine, N, N ′ -Diisopropyl-1,3-propanediamine, N, N'-dimethyl-1,6-hexanediamine, N-propylcyclopropanemethylamine, N-methylcyclohexylsilamine, N-ethylcyclohexylsilamine, N-isopropylcyclohexyl Cysylamine, N-tert-butylcyclohexylsilamine, dicyclohexylamine, N, N′-bis (3,3-dimethylbutyl) -1,2-cyclohexanediamine, 1-cyclohexylethylamine, 1,3-cyclohexanebis (methyl) Amine), N-methylallylamine , N-methyl-2-methylallylamine, diallylamine, N, N′-diethyl-2-butylene-1,4-diamine, N-allylcyclopentylamine, N-allylcycloamine, 2- (1-cyclohexene) ethylamine , 6- (dimethylamino) fulvene, bis (2-methoxyethyl) amine, methylaminoacetaldehyde dimethyl acetal, diethylaminoacetaldehyde diethyl acetal, 2-methylaminoethyl-1,3-dioxolane, diethanolamine, diisopropanolamine, N, N '-Bis (2-hydroxyethyl) ethylenediamine, 1,3-bis [tris (hydroxymethyl) methylamino] propane, N-methylglucamine, 2-methylaziridine, azetidine, pyrrolidine, 2,5-dimethylpi Loridine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 3-pyrroline, 2,5-dimethyl-3-pyrroline, piperidine, 1,2,3,6-tetotahydropyridine, 2-methylpiperidine, 2-ethylpiperidine, 3 -Methylpiperidine, 4-methylpiperidine, 4,4'-bipiperidine, 4,4'-ethylenebipiperidine, 4,4'-trimethylenebipiperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 3 , 5-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 1,4-dioxa-8-azaspiro [4.5] decane, 2-piperidinemethanol, 2-piperidineethanol, 3-hydroxypiperidine, 3 -Piperidine methanol, 4-hydroxypiperidine, 2,2,6,6-trimethyl-4 Piperidinol, 7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro [4.5] decane-2-methanol, hexamethyleneimine, heptamethyleneimine, piperazine, 2-methylpiperazine, 2, 6-dimethylpiperazine, 2,5-dimethylpiperazine, homopiperazine, acetaldehyde ammonia trimer, 1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, CYCLEN, 1,4,8 , 11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclopentadecane, HEXACYCLEN, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, dodecahydroquinoline, sparteine, 4,4-Dimethyloxadridine, 4-ethyl-2-methyl-2- (3- Tilbutyl) oxadridine, morpholine, 2,6-dimethylmorpholine, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, 1,4,10-trioxa -7,13-diazacyclopentadecane, 1,4,10,13-tetraxa-7,16-diazacyclooctadecane, thiazolidine, thiomorpholine, N-methylaniline, N-ethylaniline, N-butylaniline, diphenylamine N-phenylbenzylamine, 1,2-dianilinoethane, N-allylaniline, 2-anilinoethanol, N-ethylorthotoluidine, N-ethylmetatoluidine, N-ethylparatoluidine, 4-chloro-N-methylaniline N-methylparaanisidine, 4-aminomethylphenol, N-ethyl Til-2,3-xylidine, N-ethyl-3,4- (methylenedioxy) aniline, 2,4,6-tri-tert-butyl-N-methylaniline, N, N′-diphenyl-1,4 -Phenylenediamine, N, N'-diphenylbenzidine, 3,3 '-(hexafluoroisopropylidene) dianiline, 4,4'-(hexafluoroisopropylidene) dianiline, 2-benzylaniline, 1-amino-4-bromo Naphthalene, 1-amino-2-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 3-amino-2-naphthol, 2,2′-dithiobis (1-naphthalene), 2,3- Diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 1,1′-binaphthyl-2,2′-diamine, 1-a Noflurane, 2-aminofullerene, 2,7-diaminofullerene, 3,7-diamino-2-methoxyfullerene, 2-amino-7-bromofullerene, 2-amino-9-hydroxyfullerene, 2-amino-3- Bromo-9-hydroxyflurane, 1-aminoanthracene, 2-aminoanthracene, 9-aminophenanthrene, 9,10-diaminophenanthrene, 3-aminofluorane, 1-aminopyrene, 6-aminoclicene N, α-dimethylbenzylamine, N-benzyl-α-methylbenzylamine, N-benzylmethylamine, N-ethylbenzylmethylamine, N-isopropylbenzylmethylamine, N-butylbenzylmethylamine, N-tert- Butylbenzylmethylamine, dibenzylamine, N, N'-dibenzyl Ethylenediamine, N-methylphenethylamine, N-benzyl-2-phenethylamine, β-methylphenethylamine, N-benzylethanolamine, 2- (benzylamino) cyclohexanemethanol, α- (methylaminomethyl) benzyl alcohol, EPHEDRINE, α-diphenyl 2-pyrrolidinemethanol, 4-benzylpiperazine, 4-phenyl-1,2,3,6-tetrahydropyridine, indoline, 2-methylindoline, 1,2,3,4-tetrahydrocarbazole, 2,3-dimethylindoline , Indoline-2-carboxylic acid, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline, iminodibenzyl 5 6,11,12- tetrahydrodicyclopentadiene benz [B, F] azocine, Fenozajin or phenothiazine and the like.

  Examples of tertiary amines include trimethylamine, N, N-dimethylethylamine, N, N-diethylmethylamine, triethylamine, tripropylamine, N, N-dimethylisopropylamine, N, N-diisopropylethylamine, N, N- Dimethylbutylamine, N-methyldibutylamine, tributylamine, triisobutylamine, tripentylamine, N, N-dimethylhexylamine, trihexylamine, N, N-dimethyloctylamine, N-methyldioctylamine, trioctylamine, Triisooctylamine, triisodecylamine, N, N-dimethylundecylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyldioctadecylamine, N, N, N ′, N′-tetramethyl Jami Methane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N , N, N ′, N′-tetraethyl-1,3-propanediamine, N, N, N ′, N′-tetraethyl-1,3-butanediamine, N, N, N ′, N′-tetramethyl- 1,4-butanediamine, N, N, N ′, N′-tetramethyl-1,5-pentanediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N, N , N ′, N′-tetrabutyl-1,6-hexanediamine, tris (dimethylamino) methane, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N , N- Ethylcyclohexylamine, N-methyldicyclohexylamine, N-ethyldicyclohexylamine, N, N-dimethylcyclohexanemethylamine, triallylamine, tris (2-methylallyl) amine, N, N, N ′, N′-tetramethyl-2 -Butene-1,4-diamine, tetrakisdimethylaminoethylene, perfluoroisobutylamine, tris [2- (2-methoxyethoxy) ethyl] amine, tert-butoxybis (dimethylamino) methane, 2- (diethylamino) ethanol vinyl ether, N, N′-dimethylformamide dimethyl acetal, N, N′-dimethylformamide diethyl acetal, N, N′-dimethylformamide dipropyl acetal, N, N′-dimethylformamide diisopropyl a Settal, N, N′-dimethylformamide di-tert-butyl acetal, N, N′-dimethylformamide dineopentyl acetal, N, N′-dimethylformamide dicyclohexyl acetal, N, N-dimethylacetamide dimethyl acetal, dimethylaminoacetaldehyde Diethyl acetal, diethylaminoacetaldehyde diethyl acetal, N, N′-bis (2,2-dimethoxyethyl) methylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, 2- (diisopropylamino) ethanol, 2 -(Dibutylamino) ethanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 1-dimethylamino-2-propanol, 1-diethylamino- -Propanol, 2-dimethylamino-2-methyl-1-propanol, 5-diethylamino-2-pentanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, 1- [N, N-bis (2 -Hydroxyethyl) amino] -2-propanol, triisopropanolamine, 3- (dimethylamino) -1,2-propanediol, 3- (diethylamino) -1,2-propanediol, 3- (dipropylamino)- 1,2-propanediol, 3- (diisopropylamino) -1,2-propanediol, 2-{[2- (dimethylamino) ethyl] methylamino} ethanol, 1,3-bis (dimethylamino) -2- Propanol, N, N, N ′, N′-tetrakis (2-hydroxypro E) ethylenediamine, 2- [2- (dimethylamino) ethoxy] ethanol, PENTROL, 1-aziridineethanol, 1-methylpyrrolidine, 1-butylpyrrolidine, 1-pyrrolidino-1-cyclopentene, 1-pyrrolidino-1-cyclohexene, 1- (2-hydroxyethyl) pyrrolidine, 3-pyrrolidino-1,2-propanediol, 1-methyl-3-pyrodinol, 1-ethyl-3-pyrodinol, 1-methyl-2-pyrrolidinemethanol, 2-methyl- 1-pyrroline, 1-methylpiperidine, 1-ethylpiperidine, dipiperidinomethane, 1-ethylpiperidine, 1,1′-methylenebis (3-methylpiperidine), 4,4′-trimethylenebis (1-methyl) Piperidine), 1,2,2,6,6-pentamethylpiperidine, 1-piperidineacetaldehyde diethyl acetal, 1-piperidineethanol, 3-piperidino-1,2-propanediol, 3-hydroxy-1-methylpiperidine, 1-ethyl-3-hydroxypiperidine, 1-methyl-3-piperidinemethanol, 4,4′-trimethylenebis (1-piperidineethanol), N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexadiamine, 1,2,3 , 6-tetrahydropyridine, 1,4-dimethylpiperazine, 4- (dimethylamino) -1,2,2,6,6-pentamethylpiperazine, 1,4-bis (2-hydroxyethyl) piperazine, 1,3 , 5-tetramethylhexahydro-1,3,5-triazine, 1,3,5-tetraethylhexahydro-1,3 5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, 1,4,8,11- Tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane, TROPANE, QUINULIDINE , 3-QUILINIDINOL, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine, 4-methylmorpholine, 4-ethylmorpholine, 4- (1-cyclopenten-1-yl) morpholine, 1-morpholino- 1-cyclohexene, 1-morpholino-1-cycloheptene, 4- (2-hydroxyethyl) morpholine, -Morpholino-1,2-propanediol, 4- [2- (dimethylamino) ethyl] morpholine, 5-ethyl-1-aza-3,7-dioxabicyclo [3.3.0] octane, 1-aza -3,7-dioxabicyclo [3.3.0] octane-5-methanol, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 4,7,13 , 16,21-pentaoxa-1,10-diazabicyclo [8.8.5] tricosane, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, N , N-dimethylaniline, N-ethyl-N-methylaniline, N, N-diethylaniline, N, N-dibutylaniline, 1-phenylpiperidine, triphenylamine, N-ben Ziryl-N-ethylaniline, 2- (N-ethylanilino) ethanol, N-phenyldiethanolamine, N- (ethoxyethyl) -N-methylaniline, N, N-dimethylorthotoluidine, N, N-dimethylmetatoluidine, N , N-dimethylparatoluidine, N, N-diethylorthotoluidine, N, N-diethylmetatoluidine, N, N-diethylparatoluidine, 3-dimethylaminophenol, 3-diethylaminophenol, 2- (N-ethylmetatoluidine) F) ethanol, 4-tert-butyl-N, N-dimethylaniline, 4-bromo-N, N-dimethylaniline, 2,2 ′-(paratoluyimino) dimethanol, 4- (dimethylamino) phenethyl alcohol, N, N, N ′, N′-tetramethylbenzidine, N, N -Diglycidyl-4-glycidyloxyaniline, 2,6-diisopropyl-N, N-dimethylaniline, 4-bromo-N, N-dimethyl-3- (trifluoromethyl) aniline, N, N, 3,5-tetra Methylaniline, N, N, 2,4,6-pentamethylaniline, 4,4′-methylenebis (2,6-diisopropyl-N, N-dimethylaniline), 2,6-di-tert-butyl-4- (Dimethylaminomethyl) phenol, N, N, N ′, N′-tetramethyl-1,4-phenylenediamine, 4,4′-methylenebis (N, N-dimethylaniline), 4,4′-methylenebis (N , N-diglycidylaniline), 4,4′-vinylidenebis (N, N-dimethylaniline), leucomalachite green, 4,4′-bis (dimethyla). C) benzidolol, 1,8-bis (dimethylamino) naphthalene, 2- (dimethylamino) fullerene, N, N-dimethyl-1-phenethylamine, 3- (N-benzyl-N-methylamino) -1,2 -Propanediol, N, N-dimethylbenzylamine, N, N, N ', N'-tetrabenzylmethanediamine, N-methyldiphenylethyleneamine, tribenzylamine, N- (2-chloroethyl) dibenzylamine, N -Benzyl-N-methylethanolamine, 3-dibenzylamino-1-propanol, 2-dibenzylamino-3-phenyl-1-propanol, N-ethyl-3,3'-diphenyldipropylamine, 3-methoxy -N, N-dimethylbenzylamine, 4-bromo-N, N-diisopropylbenzylamine, 1- (Diphenylmethyl) azetidine, 1-benzyl-3-pyrroline, 1-benzyl-3-pyrrolidinol, 1-benzyl-2-pyrrolidinemethanol, 1- (3,4-dihydro-2-naphthyl) pyrrolidine, 1-methyl- 4-phenyl-1,2,3,6-tetrahydropyridine, 4-diphenylmethoxy-1-methylpiperazine, 1-benzyl-4-hydroxypiperazine, 1,3,5-tribenzylhexahydro-1,3,5 -Triazine, 4-phenylmorpholine, 2,5-dimethyl-4- (morpholinomethyl) phenol, N, N'-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, 2- Methylene-1,3,3-trimethylindoline, JULODINE, 8-hydroxyJULODINE, 5 10-dihydro-5,10-dimethylphenazine, 10 methylphenothiazine, TROGER'S BASE or 5,6-benzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8. 8] hexacosane and the like.

  Further usable amines include N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N, N′-trimethylethylenediamine, N, N-dimethyl-N′-ethylethylenediamine, N, N-diethyl-N′-methylethylenediamine, N, N, N′-triethylethylenediamine, N-methyl-1, 3-propanediamine, N-ethyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine 3 Dibutylaminopropylamine, N, N, N′-trimethyl-1,3-propanediamine, N, N, 2,2-tetraethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane, diethylenetriamine, N1 -Isopropyldiethylenetriamine, N, N, N ', N'-tetraethyldiethylenetriamine, N- (2-aminoethyl) -1,3-propanediamine, 3,3'-diamino-N-methyldipropylamine, N- ( 3-aminopropyl) -1,3-propanediamine, 3,3′-iminobis (N, N-dimethylpropylamine), SPERMIDINE, bis (hexamethylene) triamine, N, N ′, N ″ -trimethylbis ( Hexamethylene) triamine, 4- (aminomethyl) -1,8-octanedia , Triethylenetetramine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N, N′-bis (3-aminopropyl) ethylenediamine, N, N′-bis (2-aminoethyl) -1,3-propanediamine, N, N'-bis (3-aminopropyl) -1,3-propanediamine, SPERMINE, tris (2-aminoethyl) amine, tetraethylenepentamine, pentaethylenehexamine, N- Cyclohexyl-1,3-propanediamine, 2- (2-aminoethylamino) ethanol, 1- (2-aminoethyl) pyrrolidine, 2- (2-aminoethyl) -1-methylpyrrolidine, 1- (2-pyrrole) Dinylmethyl) pyrrolidine, 4- (1-pyrrolidinyl) piperidine, 4-piperidinopiperidine, 1- (2-amino) Noethyl) piperidine, 1- (3-aminopropyl) -2-pipecoline, 3-aminopiperidine, 1-methyl-4- (methylamino) piperidine, 4- (aminoethyl) piperidine, 3- (4-aminobutyl) Piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-dimethylamino-2,2,6,6-tetramethylpiperidine, 2-methyl-2-imidazoline, 4,4-dimethyl-2 -Imidazoline, 1-methylpiperazine, 1-ethylpiperazine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, 1- (2-aminoethyl) piperazine, 1, 4-bis (3-aminopropyl) piperazine, HEXETIDEN, 1,4,5,6-tetrahydropyrimidine, 1- Tylhomopiperazine, 3-aminoquinuridine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-A] pyrimidine, 1,3,4,6,7,8-hexahydro- 1-methyl-2H-pyrimido [1,2-A] pyrimidine, 4- (2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine, 5,6-dihydro-2-isopropenyl-4,4 , 6-trimethyl-4H-1,3-oxazine, N-methyl-1,2-phenylenediamine, N-phenyl-1,2-phenylenediamine, N, N-dimethyl-1,3-phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, N, N-diethyl-1,4-phenylenediamine, N4, N4-diethyl-2-methyl-1,4-phenylenediamine, 2-methoxy -N4-phenyl-1,4-phenylenediamine, N-phenyl-1,4-phenylenediamine, N-methyl-4,4'-methylenedianiline, N-phenylethylenediamine, N'-benzyl-N, N- Dimethylethylenediamine, N, N ′, N ″ -tribenzyltris (2-aminoethyl) amine, 4- (hexadecylamino) benzylamine, 4-dimethylaminobenzylamine, 4-amino-1-benzylpiperazine, 2 -Phenyl-2-imidazoline, torazoline, 2- (1-naphthylmethyl) -2-imidazoline, phentolamine, 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene, 4-benzyl-2-methyl-2-oxazoline, 4,4-dimethyl-2-phenyl-2-oxazoline, 4- Methoxymethyl-2-methyl-5-phenyl-2-oxazoline, 2-methyl-5-phenyl-2-oxazoline-4-methanol, 2,2′-bis [(4S) -4-benzyl-2-oxazoline] 2,2′-bis [(4S) -4-phenyl-2-oxazoline], 2,2′-isopropylidenebis [(4S) -4-phenyl-2-oxazoline], 2,2′-methylenebis [ (4R, 5S) -4,5-diphenyl-2-oxazoline], tetramisol, 1-phenylpiperazine, 5-phenyl-1,4,5,6-tetrahydropyrimidine, 1-benzylpiperazine, 1-cinnamylpiperazine, 1-ortho-toluylpiperazine, 1- (2,3-xylyl) piperazine, 1- (2-methoxy) piperazine, 1- (4-methoxy) piperazine 1- (2-ethoxy) piperazine, 4-morpholinoaniline, homocaine, polyethyleneimine, or polyethyleneimine graft polyalkyl (meth) acrylate copolymer, etc., primary amino group, secondary amino group and tertiary amino group Examples include amine compounds combined in the molecule.

  Furthermore, nitroamine, commercially available modified amine, and modified polyamine can also be used as the above-described amine. Examples of the nitroamine include 2-nitroaniline, 3-nitroaniline, 4-nitroaniline and 1- (4-nitrophenyl) piperazine.

  Examples of the quaternary ammonium hydroxide salt include tetramethylammonium hydroxide salt, tetraethylammonium hydroxide salt, tetrapropylammonium hydroxide salt, tetrabutylammonium hydroxide salt, triethylmethylammonium hydroxide salt, hexadecyltrimethyl hydroxide. Examples thereof include ammonium salt and benzyltrimethylammonium hydroxide salt.

  Examples of the hydrazine compound include phenyl hydrazine, 1,1-diphenyl hydrazine, 1,2-diphenyl hydrazine, 1-methyl-1-phenyl hydrazine, or orthotoluyl hydrazine.

  Examples of amide compounds include malonamide, succinamide, fumaric acid amide, adipic acid amide, NIPECITANIDE, alkyl (meth) acrylate / (meth) acryloylamide copolymer, styrene / alkyl (meth) acrylate / (meth) acryloylamide Examples thereof include a polymer, an alkyl (meth) acrylate / (meth) acryloyl morpholine copolymer, and a styrene / alkyl (meth) acrylate / (meth) acryloyl morpholine copolymer.

  Examples of the mercapto compound include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, , 9-nonanedithiol, 2-mercaptoethyl ether, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethanethiol 1,4-benzenedimethanethiol or 4,4′-thiobenzenethiol.

  Examples of the sulfide compound include ethyl disulfide, methylpropyl disulfide, isopropyl disulfide, and phenyl disulfide.

  Examples of the phosphine compound include di-tert-butylphosphine, trimethylphosphine, 1,2-bis (dimethylphosphino) ethane, triethylphosphine, tripropylphosphine, triisopropylphosphine, triisobutylphosphine, tri-tert-butylphosphine. , Trioctylphosphine, tricyclohexylphosphine, 1,4-bis (dicyclohexylphosphino) butane, phenylphosphine, diphenylphosphine, triphenylphosphine, 1,2-bis (phenylphosphino) ethane, dimethylphenylphosphine, diethylphenylphosphine Diallylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldipheny Phosphine, diphenylvinylphosphine, allyldiphenylphosphine, dicyclohexylphenylphosphine, tribenzylphosphine, triorthotoluylphosphine, trimetatoluylphosphine, triparatoluylphosphine, tris (2,4,6-trimethylphenyl) phosphine, bis (diphenylphosphino ) Methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, or 2,2′-bis (diphenylphosphino) ) -1,1′-naphthalene and the like.

  The bases B are represented by the amidines represented by the following formula (I), the imidazoles represented by the formula (II), the guanidines represented by the formula (IV), and the formula (V). It is preferred to use a base such as a phosphazene derivative. By using a base such as amidines or imidazoles, guanidines or phosphazene derivatives as the bases, the acid dissociation constant (pKa) is approximately 13 or more (in an aqueous solvent) when an alkali is used as the bases. Alternatively, when imidazoles are used, about 12 to 13 and when guanidines and phosphazene derivatives are used, the ratio is over 13.5 (both in an aqueous solvent), which is very basic and reaction during polymerization. Acts as an excellent base generator with high efficiency.

  For example, when applied to epoxy compounds, the base takes protons from water and generates hydroxide ions, which initiate the chain polymerization reaction of epoxy compounds. Since the amount of ions generated depends on the strength of the base, 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, when guanidines and phosphazene derivatives are adopted as bases constituting the base generator, pKa is about 26 to 27 (in acetonitrile (CH ₃ CN) solvent). Anionic ring-opening polymerization occurs, so if this is used, the monomer is converted into a polymer by a chain reaction.When guanidines or phosphazene derivatives are used as bases, base generators are optimal base generators for lactones and the like. When applied to a lactone or the like to form a photosensitive resin composition, a photocurable material (UV adhesive, UV ink, U V adhesion, UV coating, etc.).

  First, preferred bases include bases such as amidines represented by the following formula (I) and imidazoles represented by the following formula (II).

（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 the formula (I) that can be used as the bases B 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 imidazoles represented by the formula (II) that can be used as the bases B include imidazole, 1-methylimidazole shown in the following (II-a), and 2 shown in the following (II-b). -Methylimidazole, 2-phenylimidazole, 2-benzylimidazole, 3A, 4,5,6,7,7A-hexahydro-1H-benzimidazol-2-yl methylsulfide, 2- (4-bromophenyl) 4,5 -Dihydro-1H-imidazole, 1- [3- (triethoxysilyl) propyl] -4,5-dihydro-1H-imidazole, DL-isoamarin and the like (in addition, the number of carbons present in the above-mentioned imidazoles) 1-4 alkyl groups may contain heteroatoms such as S).

As the bases B, bases such as guanidines represented by the following formula (IV) and phosphazene derivatives represented by the following formula (V) can also be used. 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 guanidines represented by the formula (IV) that can be used as the bases B include, for example, guanidine represented by the following formula (IV-a) having a guanidine structure, and 1, 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 represented by formula (IV-d), ETBD represented by formula (IV-e), ITBD represented by 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).

  Examples of the phosphazene derivative represented by the formula (V) that can be used as the bases B include the following formula (Va), formula (Vb), formula (Vc), formula (V- d) or a compound represented by the formula (Ve) or the like (the formula (Va) to the formula (Ve) represent a proton adduct).

  In order to produce the carboxylic acid compound represented by the formula (X), the carboxylic acid represented by the formula (III) and the desired base B can be mixed for easy production. In addition, since excess carboxylic acid decomposes | disassembles by light irradiation, in order not to deactivate the base generate | occur | produced by light irradiation, when applying a carboxylic acid compound to a photosensitive resin composition as a base generator, the photosensitive resin composition In order to improve the stability, it is preferable that the mixing ratio (molar ratio) of the carboxylic acid and the bases B is such that the carboxylic acid becomes excessive. The mixing ratio is preferably an excess of carboxylic acid within the range of carboxylic acid / bases = 1.05 / 1.0 to 2.5 / 1.0, and carboxylic acid / bases = 1.05 / 1. Is more preferably 0.0 to 2.0 / 1.0, and particularly preferably carboxylic acid / bases = 1.1 / 1.0 to 1.5 / 1.0 (formula (X As shown in -2), when two carboxylic acids are added to the bases B, the carboxylic acid is doubled in the above ratio).

As 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, the type and amount of the base generator and the photosensitive resin composition are constituted. What is necessary is just to determine suitably according to the kind etc. of a base reactive compound, For example, what is necessary is just to select and apply within the range of 190-400 nm as a wavelength, and 100-10000 mJ / cm < ² > as an exposure amount, and sensitization mentioned later It is also possible to use a higher wavelength region by using an agent. Although irradiation time of irradiation light may be possible even for several seconds, it may be about 10 seconds or more, and preferably 1.5 to 20 minutes.

  Next, the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention contains, as essential components, a base generator of the present invention that undergoes a photocyclization reaction by light irradiation to generate free alkali and base, and a base-reactive compound.

  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. In particular, for example, an epoxy compound having at least one epoxy group, a silicon compound having at least one alkoxysilyl group or silanol group, an oxetane ring, and the like. Examples include oxetane compounds (oxetane resins) and the like. 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.

  Usable epoxy compounds (epoxy resins) include, for example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol poly Glycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether 1,6-hexanediol jig Sidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether, A glycidyl propoxy trimethoxysilane etc. are mentioned. These epoxy compounds may be halogenated or hydrogenated, and these epoxy compounds include derivatives. And these epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the silicon-based compound (silicon-based resin), for example, an alkoxysilane compound or a silane coupling agent can be used. Examples of alkoxysilane compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyl Examples include trimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the silane coupling agent include vinyl silane, acrylic silane, epoxy silane, amino silane, and the like. Examples of the vinyl silane include vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxysilane, and vinyl trimethoxysilane. Examples of the acrylic silane include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like. Examples of the epoxy silane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. As aminosilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane. These silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the oxetane compound (oxetane resin), a monomeric oxetane compound, a dimer oxetane compound, or the like can be used. Usable oxetane compounds include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3-ethyl-3-oxetanyl) Methyl] ester, xylylene oxetane such as 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl ) Oxetane (or 3-(((3-ethyloxetane-3-yl) methoxy) methyl) -3-ethyloxetane), 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl- 3-hydroxymethyl oxetane, oxetated phenol novolak, etc. are mentioned. These oxetane compounds may be used alone or in combination of two or more.

  Hereinafter, with respect to an example of reaction behavior with an epoxy compound when the base generator of the present invention is applied, (1) primary amine and secondary amine, (2) tertiary amine, (3) formula ( I) of amidines (in the scheme DBU) (and imidazoles represented by formula (II), guanidines represented by formula (IV), phosphazene derivatives represented by formula (V)) Give a scheme.

(1) Primary amine and secondary amine:

(2) Tertiary amine:

(3) Amidines:

  Hereinafter, specific examples of the base-reactive compound will be given. The following No. 2-1. Among the polymerized compounds (base reactive compounds) of No. 2-8, No. 2-1. 2-5, No. 2 The polymer compound 2-8 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. 2-8 is a polymer group that undergoes a desorption reaction by the action of a base and whose polarity is changed, and as a material (resist material) that performs patterning using the fact that solubility changes before and after decomposition. Can be applied. Schemes of examples of decomposition mechanisms are shown in the following scheme A and scheme B.

(Scheme A)

(Scheme B)

  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. 5-6 are polymers) are shown below.

As described above, when guanidines or phosphazene derivatives are employed as the bases B constituting the base generator, the pKa is about 26 to 27 (in acetonitrile (CH ₃ CN) solvent) and anionic ring-opening polymerization. When this is used, 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 a cyclic siloxane as a base-reactive compound is a photocurable material (UV Adhesive, UV ink, UV adhesive, UV coating, etc.). Specific examples of structures of guanidines represented by formula (IV), lactones and cyclic siloxanes that can be anionically polymerized by phosphazene derivatives represented by formula (V) are shown below as base-reactive compounds (No. 6 1-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 bases represented by formula (IV) or formula (V) as bases, it is preferable that a small amount of alcohol such as ethanol, propanol or butanol coexist, and monomer ( Base reactive compound) 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.

  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.

  Moreover, it is preferable that the photosensitive resin composition of this invention contains a thiol compound further. The thiol compound acts as a curing functional group such as epoxy when used in combination with an epoxy compound or the like. As the thiol compound, a polythiol compound having two or more thiol groups is preferably used. For example, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), dipentaerythritol hexakis. (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3 -Mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) Ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), diethylene glycol bis (3-mercaptopro) Pionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) and the like, and polythiol compounds having 2 to 5 thiol groups. Among these, in consideration of reactivity and ease of handling, pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) ) Is preferably used. These thiol compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the thiol compound used is, for example, thiol equivalent (SH equivalent) / epoxy equivalent (or oxetane equivalent) = 0.3 / 1.7 to 1.7 / 0.3 with respect to the epoxy compound or oxetane resin. Preferably, the ratio is 0.8 / 1.2 to 1.2 / 0.8. If this ratio is in the range of 0.3 / 1.7 to 1.7 / 0.3, a large amount of unreacted thiol group or epoxy group (or oxetane group) remains in the cured product. It can prevent, and can suppress the fall tendency of the mechanical property of hardened material.

  In order to form a pattern using the photosensitive resin composition according to the present invention, for example, the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is used as an appropriate solid such as a substrate. It is applied to the surface and 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 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 quickly, and sufficiently cured. In addition, since the contained base generator generates a base by a photocyclization reaction, there is no generation of carbon dioxide (CO ₂ ) as a decomposition product, there is no unevenness, and the curing is excellent in product characteristics and product value. A membrane can be provided conveniently. 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 the compound in which one base is added to the carboxylic acid represented by the formula (III). However, the present invention is not limited to this. The base generator of the invention includes those in which two carboxylic acids are added to the bases B. As an example, a compound obtained by adding two carboxylic acids of the formula (III-1) to 1,4-diazabicyclo [2.2.2] octane (1,4-ethylenepiperazine: DABCO) has the following formula (X-2) As shown.

In above-mentioned embodiment, as an example of the base reactive compound which comprises the photosensitive resin composition of this invention, No. 2-1. Although the compound of 4-6 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.

[Production Example 1]
Production of carboxylic acid (1):
The carboxylic acid represented by the formula (III-1) was produced using the following operations (1) to (3).

(1) Production of intermediate ester (1):
In a two-necked flask, 4.0 g (27 × 10 ⁻³ mol) of phthalaldehyde acid, 11.3 g of potassium carbonate (K ₂ CO ₃ ) and 4.1 g of methyl iodide (CH ₃ I) are dissolved in 100 ml of acetone. And then refluxed for 5 hours. The product was filtered, concentrated and dried under reduced pressure to obtain a yellow liquid of intermediate ester (1) represented by the following formula (H-1) in a yield of 4.0 g and a yield of 93%.

(2) Production of intermediate ester (2):
In a two-necked flask, 10.0 g of the phosphonium salt represented by the formula (P) and 6.0 g of potassium ter-butoxide ((CH ₃ ) ₃ COK, t-BuOK) are further added, and 40 ml of tetrahydrofuran is further added at room temperature for 1 hour. Stir. After stirring, 4.0 g of the intermediate ester (1) obtained in (1) and 20 ml of tetrahydrofuran were added, and further mixed and stirred at room temperature for 6 hours. After stirring, the reaction was stopped by adding hydrochloric acid, followed by extraction three times with dichloromethane and three times with water, and then ethyl acetate and hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 1/5. A yellow liquid of intermediate ester (2) represented by the following formula (H-2) was obtained in a yield of 3.3 g and a yield of 77%.

(3) Production of carboxylic acid (1):
In a two-necked flask, 3.3 g of the intermediate ester (2) obtained in (2) and 60 ml of a mixed solution in which water and methanol were mixed at a ratio of water / methanol = 1/3 were added. Further, 4.0 g of potassium hydroxide (KOH) and 40 ml of a mixed solution of water and methanol mixed in water / methanol = 1/3 were put into a vial, and this was put into a two-necked flask and then refluxed for 6 hours. . After refluxing, hydrochloric acid was added to stop the reaction, and the mixture was extracted 3 times with dichloromethane and 3 times with water, and then ethyl acetate and hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 2/1. A white solid of the carboxylic acid represented by the formula (III-1) was obtained in a yield of 1.2 g and a total yield of 28%.

[Production Example 2]
Production of carboxylic acid (2):
Carboxylic acid represented by the formula (III-2) was produced using the following operations (1) and (2).

(1) Production of intermediate ester (3):
In a two-necked flask, 12 g (0.033 mol) of the phosphonium salt represented by the formula (P) and 3.7 g (0.033 mol) of potassium ter-butoxide ((CH ₃ ) ₃ COK, t-BuOK) were added, and further 40 ml of tetrahydrofuran. And mixed and stirred at room temperature for 6 hours. After stirring, 5.0 g (0.022 mol) of methyl 2-formyl-3,5-dimethyloxybenzoate represented by the following formula (Q) and 20 ml of tetrahydrofuran were added, stirred for 12 hours under reflux, and then quenched with hydrochloric acid. After extracting 3 times with dichloromethane and 3 times with water, ethyl acetate and hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 1/7 and represented by the following formula (H-3). The dimethoxy intermediate ester was obtained in a crude yield of 0.81 g and a crude yield of 16%.

(2) Production of carboxylic acid (2):
In a two-necked flask, 0.81 g of the methoxy intermediate ester obtained in (1) and 60 ml of a mixed solution in which water and methanol were mixed with water / methanol = 1/3 were added. Further, 2.0 g of potassium hydroxide (KOH) (5 times mol of the intermediate ester) and 40 ml of a mixed solution in which water and methanol are mixed with water / methanol = 1/3 are put into a vial, and this is a two-necked flask. And then refluxed for 4 hours. After refluxing, hydrochloric acid was added to stop the reaction, and the mixture was extracted 3 times with dichloromethane and 3 times with water, and then ethyl acetate and hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 1/5. A brown solid of the carboxylic acid represented by the formula (III-2) was obtained in a yield of 0.51 g and a total yield of 14%.

[Example 1]
Production of base generator (1):
0.30 g (1.8 × 10 ⁻³ mol) of the carboxylic acid represented by the formula (III-1) obtained by the above method and 1,5,7 which is a base and represented by the formula (IV-c) -Triaza-bicyclo [4.4.0] dec-5-ene (TBD) 0.12g (0.8 * 10 < ^-3 > mol) was put in dimethyl ether, mixed, and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed to obtain a white solid of the base generator of the present invention represented by the following formula (X-1) in a yield of 0.18 g and a yield of 69%.

[Example 2]
Production of base generator (2):
0.60 g (3.6 × 10 ⁻³ mol) of the carboxylic acid represented by the formula (III-1) obtained by the above method, and DABCO (1, which is a base and represented by the following formula (B-1)) 0.10 g (0.8 × 10 ⁻³ mol) of 4-diazabicyclo [2.2.2] octane / 1,4-ethylenepiperazine) was mixed in dimethyl ether and reacted at room temperature for 3 hours. After completion of the reaction, the solvent was removed to obtain a colorless viscous liquid of the base generator of the present invention represented by the above formula (X-2) in a yield of 0.11 g and a yield of 28%.

[Example 3]
Production of base generator (3):
The method obtained in the formula (III-1) to the indicated carboxylic acid 0.20g (1.2 × 10 ^-
3 mol) and diazabicycloundecene (DBU) 0 which is a base and represented by the formula (Ib)
. 15 g (0.98 × 10 ⁻³ mol) was mixed in dimethyl ether and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed to obtain a colorless viscous liquid of the base generator of the present invention represented by the following formula (X-3) in a yield of 0.25 g and a yield of 61%.

[Example 4]
Production of base generator (4):
0.05 g (0.22 × 10 ⁻³ mol) of the carboxylic acid represented by the formula (III-2) obtained by the above method and 1,5,7 which is a base and represented by the formula (IV-c) -Triaza-bicyclo [4.4.0] dec-5-ene (TBD) 0.03 g (0.21 × 10 ⁻³ mol) was mixed in ethanol, and the mixture was stirred at room temperature for 3 hours to be reacted. . After completion of the reaction, the solvent was removed to obtain a light brown solid of the base generator of the present invention represented by the following formula (X-4) in a yield of 0.023 g and a yield of 23%.

Confirmation of photodegradation behavior (UV spectrum measurement):
About the base generator obtained in Example 1 thru | or Example 4, the methanol was used as a solvent and the photodegradation behavior was confirmed using the following measuring method.

(Measuring method)
The methanol solution of the base generator of Examples 1 to 4 whose concentrations are shown in Table 1 was irradiated with light having a wavelength of 254 nm, and an ultraviolet-visible spectrophotometer (MultiSpec-1500 / manufactured by Shimadzu Corporation) was used. The change with time of the UV spectrum was confirmed. The results are shown in FIG. 1 (Example 1), FIG. 2 (Example 2), FIG. 3 (Example 3) and FIG. 4 (Example 4).

(Methanol solution concentration)

Table 2 shows the molar extinction coefficient (ε ₂₅₄ ) (l / cm · mol) and the maximum absorption wavelength λ _max (nm) at ₂₅₄ nm.

(Molar extinction coefficient and maximum extinction coefficient)

  As shown in FIGS. 1 to 4, the base generators of the present invention obtained in Examples 1 to 4 changed the absorption with the exposure amount of light irradiation, and the photodegradation behavior was confirmed. .

  FIG. 5 is a diagram comparing the photodegradation behavior of the base generators obtained in Example 1 and Example 4. As shown in FIG. 5, the base generator of Example 4 has a peak on the longer wavelength side as compared with the base generator of Example 1, and the photodegradation behavior of the base generator of Example 4 is that of Example 1. It was confirmed that it was faster than the base generator. This difference is considered to be due to the difference in the structures of the carboxylic acids shown in the formulas (III-1) and (III-2).

Confirmation of photocyclization in solution:
In a quartz cell, 0.07 g of the base generator obtained in Example 1 and spectroscopic methanol were placed, mixed with stirring, and then irradiated with monochromatic light of 254 nm at an exposure amount of 50000 mJ / cm ² . After irradiation, the photocyclized product was isolated by column chromatography, and ¹ H-NMR measurement and Mass-spectrum measurement were performed. The result of ¹ H-NMR is shown below. From this result, it was confirmed that a photocyclization reaction was performed in the solution and carbon dioxide gas (CO ₂ ) was not generated.

(Results of ¹ H-NMR)
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.5 (d, 3H, —CH ₃ ), 2.9 (m, 2H, —CH ₂ —), 4.7 (m, 1H, -CH-), 7.5 (m, 3H, Ar-H), 8.1 (d, 1H, Ar-H)

  Moreover, in the result of ESI + by Mass-spectrum measurement, the measured value almost coincided with 185.05561 while the theoretical value was 185.05785.

Confirmation of base generation ability by light irradiation:
After putting the methanol solution prepared in 2 ml (8.9 × 10 ⁻³ mol / L) of the base generator obtained in Example 1 into a quartz cell and irradiating a predetermined amount of light with a wavelength of 254 nm, photodecomposition was performed. The UV spectrum was measured when 2 mL of phenol red solution that had been adjusted to 4.9 × 10 ⁻⁵ mol / L in advance was added to this solution. The results are shown in FIG.

  FIG. 6 is a diagram showing changes in the UV spectrum. As shown in FIG. 6, the base generator obtained in Example 1 decreased the absorption around 424 nm and increased the absorption near 562 nm as the exposure amount increased. It was confirmed that a free base was generated by irradiation.

Confirmation of photocyclization reaction and base generation:
In a quartz cell containing a stirrer, 0.07 g of the base generator obtained in Example 1 and 4 ml of spectroscopic methanol were added. After stirring with a stirrer, light having a wavelength of 254 nm was applied with an exposure amount of 50000 mJ / cm. After irradiation as ² , the photocyclization was confirmed by measurement with ¹ H-NMR. The results are shown in FIG.

FIG. 7 is a diagram showing a ¹ H-NMR spectrum. As shown in FIG. 7, the peak of the HN ⁺ group that existed before the exposure disappeared, the peak derived from the aromatic ring of the cyclized product was 7.5 ppm and 8.1 ppm, and the peak derived from the methine group was 4.7 ppm. In addition, it was confirmed that the peak derived from the methylene group was 2.9 ppm and the peak derived from the methyl group was 1.5 ppm, respectively, and it was confirmed that photocyclization occurred without generation of carbon dioxide gas.

Confirmation of photodegradation behavior in polystyrene:
A photosensitive resin by containing 0.03 g of the base generator obtained in Example 1 (30 parts by mass with respect to 100 parts by mass of polystyrene) with respect to 0.1 g of polystyrene (manufactured by Aldroch, Mw = 28000). It was set as the composition. Such a photosensitive resin composition is dissolved in chloroform to form a sample solution. This sample solution is 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 form a film. Produced. The film was irradiated with monochromatic light of 254 nm with exposure amounts of 0, 8000, 16000, 24000, and 36000 mJ / cm ² , and the reaction was monitored by FT-IR.

From the literature value, a cyclic ester derived from the peak _{(V C = O) = 1720cm} -1, COO - derived peak _(V COO-) a = 1374cm ^-1. FIG. 8 shows the relationship between the exposure amount at 1720 cm ⁻¹ and the increase rate of the peak area ratio, and FIG. 9 shows the relationship between the exposure amount at 1374 cm ⁻¹ and the decrease rate of the peak area ratio. The increase rate and decrease rate of the peak area ratio were calculated based on the area of exposure amount = 0 mJ / cm ² .

As shown in FIG. 8, at 1720 cm ⁻¹ , the peak area ratio increased as the exposure amount increased, and it was confirmed that photocyclization occurred without generating carbon dioxide gas. This is apparent from the fact that the peak area ratio decreases as the exposure amount increases at 1374 cm ⁻¹ as shown in FIG.

[Example 5]
Production of photosensitive resin composition (1):
Obtained in Example 1 against 0.1 g of polyglycidyl methacrylate (PGMA, M _W = 61000, M _W / M _n = 2.2), which is an epoxy compound represented by the formula (No. 4-12) 0.0050 g (Example 5-1), 0.010 g (Example 5-2), 0.015 g (Example 5-3) (in order, 5.0 parts per 100 parts by mass of PGMA) (10.0, 15.0 parts by mass) (1.6, 3.2, 4.8 mol% with respect to the monomer unit of PGMA) was contained to obtain the photosensitive resin composition of the present invention.

[Example 6]
Production of photosensitive resin composition (2):
Obtained in Example 2 against 0.2 g of polyglycidyl methacrylate (PGMA, M _W = 15000, M _W / M _n = 2.2), which is an epoxy compound represented by the formula (No. 4-12) 0.0030 g (Example 6-1), 0.0062 g (Example 6-2), and 0.012 g (Example 6-3) (in order, 1.5 parts per 100 parts by mass of PGMA) , 3.0, 6.0 parts by mass) (0.5, 1.0, 2.0 mol% with respect to the monomer unit of PGMA), the photosensitive resin composition of the present invention was obtained.

[Example 7]
Production of photosensitive resin composition (3):
Obtained in Example 3 against 0.2 g of polyglycidyl methacrylate (PGMA, M _W = 15000, M _W / M _n = 2.2) which is an epoxy compound represented by the formula (No. 4-12) 0.0022 g (Example 7-1), 0.0044 g (Example 7-2), 0.0088 g (Example 7-3) (in order, 1.14 to 100 parts by mass of PGMA) , 2.2, 4.4 parts by mass) (0.5, 1.0, 2.0 mol% with respect to the monomer unit of PGMA), the photosensitive resin composition of the present invention was obtained.

[Test Example 1]
Confirmation of photoinsolubilization behavior (1) (depending on heating temperature):
The photosensitive resin composition obtained in Example 5-2 was dissolved in 1.5 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 1 minute to produce a film having a thickness of 0.6 μm. This film was irradiated with monochromatic light of 254 nm, post-baked at 70 ° C. for 15 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed with the post-baking temperature changed to 80 ° C., and a 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 shown in FIG. 10A, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating temperature was increased.

[Test Example 2]
Confirmation of photoinsolubilization behavior (2) (depending on addition amount):
The photosensitive resin composition obtained in Example 5-1 (1.6 mol% based on the monomer unit of PGMA) was dissolved in 1.5 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 1 minute to produce a film having a thickness of 0.6 μm. The film was irradiated with monochromatic light of 254 nm, post-baked at 80 ° C. for 15 minutes, developed with chloroform for 30 seconds, and the remaining film thickness was measured. And the same operation was implemented with respect to the photosensitive resin composition obtained in Example 5-2 (similarly 3.2 mol% thing), and the relationship between each exposure amount and a residual film rate (sensitivity) Curve). The obtained sensitivity curve is shown in FIG. As shown in FIG. 10B, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the amount of the base generator added was increased.

[Test Example 3]
Confirmation of photoinsolubilization behavior (3) (depending on heating time):
The photosensitive resin composition obtained in Example 5-1 was dissolved in 1.5 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 1 minute to produce a film having a thickness of about 0.6 μm. This film was irradiated with monochromatic light of 254 nm, post-baked at 80 ° C. for 10 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed with the post-baking time changed to 15 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. As shown in FIG. 10C, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating time was increased.

[Test Example 4]
Confirmation of photoinsolubilization behavior (4) (depending on heating temperature):
The photosensitive resin composition obtained in Example 6-2 was dissolved in 1.5 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 100 ° C. for 1 minute to produce a film having a thickness of 0.6 μm. This film was irradiated with monochromatic light of 254 nm, post-baked at 80 ° C. for 30 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed with the post-baking temperature changed to 100 ° 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 shown in FIG. 11A, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating temperature was increased.

[Test Example 5]
Confirmation of photoinsolubilization behavior (4) (addition amount dependency):
The photosensitive resin composition obtained in Example 6-1 (0.5 mol% based on the monomer unit of PGMA) was dissolved in 1.5 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 100 ° C. for 1 minute to produce a film having a thickness of 0.6 μm. This film was irradiated with monochromatic light of 254 nm, postbaked at 100 ° C. for 30 minutes, developed with chloroform for 30 seconds, the thickness of the remaining film was measured, and the relationship between the exposure amount and the remaining film ratio (Sensitivity curve) was created. The obtained sensitivity curve is shown in FIG. As shown in FIG. 11 (B), it was confirmed that the photosensitive resin composition of Example 6-1 exhibited photoinsolubilization behavior.

[Test Example 6]
Confirmation of photoinsolubilization behavior (6) (depending on heating time):
The photosensitive resin composition obtained in Example 6-1 was dissolved in 1.5 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 1 minute to produce a film having a thickness of about 0.6 μm. This film was irradiated with monochromatic light of 254 nm, post-baked at 100 ° C. for 15 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed with the post-baking time changed to 30 minutes and 45 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. As shown in FIG. 11C, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating time was increased.

[Test Example 7]
Confirmation of photoinsolubilization behavior (7) (depending on heating temperature):
The photosensitive resin composition obtained in Example 7-2 was dissolved in 1.5 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 100 ° C. for 1 minute to produce a film having a thickness of 0.6 μm. The film was irradiated with monochromatic light of 254 nm, post-baked at 80 ° C. for 15 minutes, developed with chloroform for 30 seconds, and the remaining film thickness was measured. The same operation was performed with the post-baking temperature changed to 100 ° 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 shown in FIG. 12A, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating temperature was increased.

[Test Example 8]
Confirmation of photoinsolubilization behavior (8) (addition amount dependency):
The photosensitive resin composition obtained in Example 7-1 (1.6 mol% based on the monomer unit of PGMA) was dissolved in 1.5 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 100 ° C. for 1 minute to produce a film having a thickness of 0.6 μm. This film was irradiated with monochromatic light of 254 nm, post-baked at 100 ° C. for 15 minutes, developed with chloroform for 30 seconds, and the thickness of the remaining film was measured. Then, the same operation was performed on Example 7-2 (similarly 1.0 mol%), and a relationship (sensitivity curve: heating temperature dependency) between the exposure amount and the remaining film ratio was created for each. did. The obtained sensitivity curve is shown in FIG. As shown in FIG. 12B, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the addition amount of the base generator was increased.

[Test Example 9]
Confirmation of photoinsolubilization behavior (9) (depending on heating time):
The photosensitive resin composition obtained in Example 7-2 was dissolved in 1.5 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 1 minute to produce a film having a thickness of about 0.6 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. The same operation was performed with the post-baking time changed to 15 minutes, and a relationship (sensitivity curve) between the exposure amount and the remaining film rate was created for each. The obtained sensitivity curve is shown in FIG. As shown in FIG. 12C, it was confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) was improved as the heating time was increased.

[Test Example 10]
Comparison of base generators:
The photosensitive resin compositions obtained in Example 6-1 and Example 7-1 were each dissolved in 1.5 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 1 minute to produce a film having a thickness of about 0.6 μm. This film was irradiated with monochromatic light of 254 nm, postbaked at a temperature of 100 ° C. for 30 minutes, developed with chloroform for 30 seconds, and the remaining film thickness was measured. The relationship (sensitivity curve) was created. The results are shown in FIG.

  FIG. 13 is a diagram comparing the sensitivity evaluation results of the photosensitive resin compositions obtained in Example 6-1 and Example 7-1. When compared under the same film forming conditions, it was confirmed that Example 6-1 showed insolubilization behavior with a smaller exposure amount, and the afterimage rate increased.

[Test Example 11]
Confirmation of photoinsolubility behavior of photosensitive resin composition:
The photosensitive resin composition obtained in Example 6-2 was dissolved in 1.5 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 1 minute to produce a film having a thickness of about 0.6 μm. This film was irradiated with monochromatic light of 254 nm, irradiated with an exposure amount of 8000 mJ / cm ² , heated at a post-baking temperature of 100 ° C. for 15, 30, 60 minutes, and the reaction was monitored by FT-IR.

From the literature values, the peak derived from the epoxy group = 907 cm ⁻¹ . FIG. 14 shows the relationship between the heating time at 907 cm ⁻¹ and the reduction rate of the peak area ratio. In addition, the reduction rate of the peak area ratio was calculated by setting the area of heating time = 0 minutes as 1.

As shown in FIG. 14, the peak area ratio at 907 cm ⁻¹ decreases as the heating time increases. It was confirmed that the epoxy group was cured and insolubilized by the reaction between the epoxy group and the base generated by light irradiation.

  In addition, about the film | membrane concerning an Example evaluated by [Test Example 1]-[Test Example 11] and the test example (refer also to [Test Example 14]) mentioned later, the unevenness | corrugation by carbon dioxide gas generation | occurrence | production in the case of exposure is also carried out. I couldn't see it.

[Production Example 3]
Production of carboxylic acid (3):
The carboxylic acid represented by the formula (III-3) was produced using the following operations (1) and (2).

(1) Production of intermediate (1):
The eggplant flask was charged with 50 ml of acetonitrile (CH ₃ CN), 8.0 g (454 mmol) of 7-methoxy-1-tetralone represented by the following formula (R), and 9.6 g (542 mmol) of N-bromosuccinimide (NBS), and protected from light. The mixture was mixed and stirred for 30 hours. After stirring, the mixture was extracted with an aqueous sodium thiosulfate solution, and then ethyl acetate and hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 1/7, and an intermediate represented by the following formula (H-4) ( The yellow solid of 1) was obtained in a yield of 7.7 g and a yield of 67%.

(2) Production of intermediate (2):
In a two-necked flask, 8.7 g (234 mmol) of the phosphonium salt represented by the formula (P), 2.0 g (178 mmol) of potassium ter-butoxide ((CH ₃ ) ₃ COK, t-BuOK) were added, and 40 ml of tetrahydrofuran was further added. Mix and stir for 6 hours at room temperature. After stirring, 4.7 g (185 mmol) of the intermediate represented by the formula (H-4) obtained in (1) and 20 ml of tetrahydrofuran were added and stirred at room temperature for 24 hours, and then the reaction was stopped by adding hydrochloric acid. Then, ethyl acetate and hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 1/5 to obtain an intermediate (2) represented by the following formula (H-5). Obtained 2.69 g, 54% yield.

(3) Production of carboxylic acid:
A four-necked flask was charged with 0.34 g (0.014 mol) of magnesium (Mg) and 40 ml of tetrahydrofuran, and mixed and stirred at room temperature for 10 minutes. After stirring, 2.69 g (0.010 mol) of the intermediate (2) represented by the formula (H-5) obtained in (2) in 20 ml of tetrahydrofuran was added to this four-necked flask at room temperature under a nitrogen atmosphere. The solution was refluxed with heating for 1 hour. Moreover, after putting dry ice and the reaction liquid after heating to reflux in a beaker and leaving to stand until the dry ice is dissolved, hydrochloric acid is added to stop the reaction, extraction with dichloromethane is performed three times, and then ethyl acetate and hexane are mixed with ethyl acetate / hexane. Separation by column chromatography using a developing solvent of hexane = 1/5 gave a yellow solid of carboxylic acid represented by the formula (III-3) in a yield of 0.859 g and a yield of 37%.

[Example 8]
Production of base generator (5):
0.25 g (1.05 mmol) of the carboxylic acid represented by the formula (III-3) obtained by the above method and 1,5,7-triaza-bicyclo [base] represented by the formula (IV-c) 4.4.0] Dec-5-ene (TBD) 0.14 g (1.00 mmol) was mixed in 50 ml of ether, and the mixture was stirred at room temperature for 1 hour to be reacted. After completion of the reaction, the solvent was removed, and a yellow solid of the base generator of the present invention represented by the following formula (X-5) was obtained in a yield of 0.31 g (0.82 mmol) and a yield of 80%.

(Measurement of decomposition point)
About the base generator obtained in Example 1, Example 4, and Example 8, the decomposition point (thermal decomposition temperature) was measured with the differential thermothermal weight simultaneous measurement apparatus (Tg-DTA). The results are shown in Table 3. As shown in Table 3, the base generator shown in Example 8 using the carboxylic acid shown in Formula (III-3) showed a high decomposition point of 320 ° C. In addition, although the decomposition point of any base generator was 200 degreeC or more, in the photosensitive resin composition which requires high temperature heating (around 200 degreeC), such as photosensitive polyimide, a decomposition point exceeds 200 degreeC. The base generator according to the present invention is suitable.

(Disassembly point)

Confirmation of photodegradation behavior (UV spectrum measurement):
About the base generator obtained in Example 8, methanol was used as a solvent and the photodegradation behavior was confirmed using the following measurement method.

(Measuring method)
A methanol solution of the base generator of Example 8 adjusted to 6.0 × 10 ⁻⁵ mol / l was irradiated with light having wavelengths of 254 nm and 313 nm, and an ultraviolet-visible spectrophotometer (MultiSpec-1500 / manufactured by Shimadzu Corporation) ) Was used to confirm the time course of the UV spectrum. The results are shown in FIG. 15 (254 nm) and FIG. 16 (313 nm). As shown in FIGS. 15 and 16, the base generator of the present invention obtained in Example 8 was changed in absorption with the exposure amount of light irradiation, and the photodegradation behavior could be confirmed. Note that the peak near 315 nm shown in FIGS. 15 and 16 is a peak generated when a cyclization reaction occurs, and that the base generator of Example 8 is subjected to a photocyclization reaction by exposure. It could be confirmed.

FIG. 17 shows the base generator of Example 8 and the cyclohexylamine salt (Example X) represented by the following formula (X-6) comprising carboxylic acid and cyclohexylamine represented by formula (III-2). A methanol solution having a concentration of 6.0 × 10 ⁻⁵ mol / l was irradiated with light of 254 nm, and the exposure amount was 0, 10, 20, 40, 80, 160, 320, 640 mJ / cm for Example 8. ^{2 and 0} , 150, 300, 600, 1200 mJ / cm ² for Example X, and the results of confirming the peak intensity at 315 nm for Example 8 and 318 nm for Example X (exposure amount and peak intensity FIG. As shown in FIG. 17, photodegradation behavior occurs in both cases, but with the base generator of Example 8, it can be confirmed that the photocyclization reaction is almost completed with a relatively small exposure (about 320 mJ / cm ² ). It was.

[Example 9]
Production of photosensitive resin composition (4):
0.1 g of poly (3- (trimethoxysilyl) propyl methacrylate (PMAS, M _W = 14000, M _W / M _n = 1.67), which is a silicon-based compound represented by the formula (No. 5-6) On the other hand, the base generator obtained in Example 1 is contained in an amount of 0.0050 g (5.0 parts by mass with respect to 100 parts by mass of PMAS) (4.0 mol% with respect to the monomer unit of PMAS). A photosensitive resin composition was obtained.

[Example 10]
Production of photosensitive resin composition (5):
0.1 g of poly (3- (trimethoxysilyl) propyl methacrylate (PMAS, M _W = 14000, M _W / M _n = 1.67), which is a silicon-based compound represented by the formula (No. 5-6) On the other hand, the base generator obtained in Example 4 was added in an amount of 0.0064 g (6.4 parts by mass with respect to 100 parts by mass of PMAS) (4.0 mol% with respect to the monomer unit of PMAS). A photosensitive resin composition was obtained.

[Example 11]
Production of photosensitive resin composition (6):
0.1 g of poly (3- (trimethoxysilyl) propyl methacrylate (PMAS, M _W = 14000, M _W / M _n = 1.67), which is a silicon-based compound represented by the formula (No. 5-6) On the other hand, the base generator obtained in Example 8 was added in an amount of 0.0062 g (6.2 parts by mass with respect to 100 parts by mass of PMAS) (4.0 mol% with respect to the monomer unit of PMAS). A photosensitive resin composition was obtained.

[Test Example 12]
Curing test (heating temperature dependence)
The photosensitive resin compositions obtained in Example 9, Example 10, and Example 11 were dissolved in 1.0 ml of tetrahydrofuran (THF) to prepare sample solutions. This sample solution was bar-coated on a glass substrate to form a film, heated at 50 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 14 μm. The coating film hardness after heating at room temperature, 50 ° C., and 70 ° C. for 30 minutes with 254 nm monochromatic light, exposure doses of 0 (blank), 100, 1000, and 10000 mJ / cm ² was applied to this coating film as JIS K5600-5. -4 was measured for pencil hardness and compared and evaluated. The results are shown in FIG. 18 (Example 9), FIG. 19 (Example 10), and FIG. 20 (Example 11).

18 to 20 are diagrams showing the relationship between the exposure dose and the pencil hardness in Test Example 12, and it was confirmed that curing proceeds as the exposure dose is increased and the heating temperature is increased. In addition, the photosensitive resin composition of Example 11 had good sensitivity, showed a tendency to be cured at a lower exposure amount or lower temperature than the others, and a hardness of 4H was obtained (heating temperature). 50 ° C. and 70 ° C., exposure amount 10,000 mJ / cm ² ).

[Test Example 13]
Curing test (heating time dependence)
The photosensitive resin compositions obtained in Example 9, Example 10, and Example 11 were dissolved in 1.0 ml of tetrahydrofuran (THF) to prepare sample solutions. This sample solution was bar-coated on a glass substrate to form a film, heated at 50 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 14 μm. The coating film hardness after heating at 50 ° C. for 15 minutes, 30 minutes, and 60 minutes with 254 nm monochromatic light, exposure doses of 0 (blank), 100, 1000, and 10000 mJ / cm ² is applied to this coating film. The pencil hardness was measured according to 5-4, and compared and evaluated. The results are shown in FIG. 21 (Example 9), FIG. 22 (Example 10), and FIG. 23 (Example 11). Moreover, what compared the result of Example 9, Example 10, and Example 11 about what made heating time 60 minutes is shown in FIG.

21 to 23 are diagrams showing the relationship between the exposure amount and the pencil hardness in Test Example 13, and FIG. 24 is a pencil of the photosensitive resin composition obtained in Examples 9 to 11. It is the figure which compared the result of the hardness measurement. It was confirmed that curing progressed as the exposure amount was increased and the heating time was increased. In addition, the photosensitive resin composition of Example 11 has good sensitivity, has a tendency to be cured with a smaller exposure amount (particularly see FIG. 24) or a shorter heating time than the others, and has a maximum hardness of 4H. (Exposure amount 10,000 mJ / cm ² ) was obtained.

[Example 12]
Production of photosensitive resin composition (7):
0.2 g of poly (3- (trimethoxysilyl) propyl methacrylate (PMAS, M _W = 14000, M _W / M _n = 1.67), which is a silicon-based compound represented by the formula (No. 5-6) On the other hand, the photosensitive resin composition of the present invention was obtained by containing 0.01 g (5 parts by mass with respect to 100 parts by mass of PMAS) of the base generator obtained in Example 8.

[Reference Example 1]
Production of photosensitive resin composition (8):
(1) Production of base generator:
As a carboxylic acid, 2.0 g (7.9 mmol) of ketoprofen and 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene (TBD) which is a base and represented by the formula (IV-c) 1.1 g (7.9 mmol) was added to tetrahydrofuran as a solvent, mixed, and stirred at room temperature for 1 hour for reaction. After completion of the reaction, the solvent was removed, ether was added and stirred, followed by decantation to remove unreacted ketoprofen and TBD. After removal, drying under reduced pressure was performed to obtain 1.8 g of a white solid of a base generator represented by the following formula (Y) in a yield of 58%.

(2) Production of photosensitive resin composition:
0.2 g of poly (3- (trimethoxysilyl) propyl methacrylate (PMAS, M _W = 14000, M _W / M _n = 1.67), which is a silicon-based compound represented by the formula (No. 5-6) On the other hand, the photosensitive resin composition was obtained by containing 0.01g (5 mass parts with respect to 100 mass parts of PMAS) of the base generator obtained by (1).

[Test Example 14]
Confirmation of carbon dioxide generation:
The photosensitive resin composition obtained in Example 12 and Reference Example 1 was dissolved in 0.5 ml of methanol to obtain a sample solution. This sample solution was dried under reduced pressure for 3 minutes to remove the solvent (methanol) as much as possible, and then bar-coated on a glass substrate to form a film. After film formation, with quartz glass sandwiched from above and fixed with clips, the exposure was set to 0 (blank), 1000, and 10000 mJ / cm ² , exposure with a Hg-Xe lamp (no filter), and 50 ° C. × 30 Heating was performed for minutes, and the film was visually observed to confirm whether carbon dioxide gas was generated. Moreover, about what was formed into a film, the pencil hardness in the same exposure and heating conditions was measured, and the pencil hardness corresponding to irradiation time was confirmed. The results are shown in Table 4.

(result)

As shown in Table 4, with respect to the base generator of Reference Example 1 using ketoprofen as the carboxylic acid, carbon dioxide gas is generated when the exposure dose is 1000, 10000 mJ / cm ² . On the other hand, it was confirmed that the base generator of Example 12 did not generate carbon dioxide gas even at the same exposure amount and exhibited pencil hardness of 2H and 3H.

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 (7)

A carboxylic acid compound comprising a carboxylic acid and a base and represented by the following formula (X):

(In formula (X), R ₁ , R ₂ and R ₃ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group. , Sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or an organic group, which may be the same or different, and R ₁ , R ₂ , and R ₃ are two of them. The above may combine to form a cyclic structure, and may include a heteroatom bond, and R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, halogen, hydroxyl group, mercapto Group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, a Amino group, an alkoxy group, an amido group or an organic group, which may be different even in the same _{.R 4, R 5, R 6} , R 7 are those two or more ring structure by bonding with It may be formed and may contain a heteroatom, and B represents a base that serves as a base.) It consists of following formula (X '), The carboxylic acid compound of Claim 1 characterized by the above-mentioned.

(In the formula (X ′), R ₁ , R _2, R ₄ , R ₅ and R ₆ are the same as the group shown in the formula (X), and R ₁ and R ₂ are bonded to form a cyclic group. A structure may be formed, and a bond of a hetero atom may be included, and two or more of R ₄ , R ₅ , and R ₆ may be bonded to form a cyclic structure. (It may contain an atom, and n represents an integer of 0 to 6.)   A base generator comprising the carboxylic acid compound according to claim 1 or 2. The base is at least one selected from the group consisting of compounds represented by the following formula (I), formula (II), formula (IV) and formula (V). Base generator.

(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.)

(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).)   A photosensitive resin composition comprising the base generator according to claim 3 or 4 and a base-reactive compound.   6. The photosensitive resin composition according to claim 5, wherein the base-reactive compound is at least one selected from the group consisting of an epoxy compound, a silicon compound, and an oxetane compound.   Furthermore, the thiol compound is included, The photosensitive resin composition of Claim 5 or Claim 6 characterized by the above-mentioned.

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