JP2010105930A - Photobase generator and photo-curing type resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photobase generator suitable for the photo-curing of anion curing type resins such as epoxy resins and polyimide resins, and to provide a photo-curing type resin composition using the same. <P>SOLUTION: The photobase generator includes 2-aminotropon derirative or a tantomer thereof wherein the total value of substituent constants of substituents exceeds 0 in formula (1), and the photo-curing type resin composition contains the photobase generator and the anion curing type resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photobase generator and a photocurable resin composition.

  Resin photocuring technology has advantages over conventional thermosetting technology in that it can be cured at low temperature for a short time, as well as fine processing by photopatterning. In particular, it is widely used in the field of electronic materials. Resin photocuring techniques are roughly classified into three types: radical type, cationic type, and anionic type. Conventionally, the radical type is the mainstream among these, but the (meth) acrylic acid polymer used in the radical type generally has a large cure shrinkage and there is room for improvement in heat resistance and adhesiveness.

  In the cationic type, a photoacid generator is used, and a number of compounds have been developed. In the anionic type, a photobase generator is used, and a compound that generates an amine by light has been reported. For example, carbamic acid derivatives are known (Non-Patent Document 1 and Patent Document 1). However, this technique has a problem that carbon dioxide gas is produced as a by-product with exposure, and bubbles are generated in the cured product, resulting in fine processing and the like. Is a serious drawback.

  Moreover, the example of the photobase generator which carbon dioxide gas does not by-produce is described in patent document 2 and 3 etc., These contain an ionic component. This ionic component remains not a little after exposure, and lowers the insulating properties. For this reason, it is difficult to apply to electronic materials that require strict insulation reliability.

By the way, it is already known that when an aminotropone is irradiated with ultraviolet rays as a photobase generator, an intramolecular cyclization reaction represented by the following formula (3) proceeds (Patent Document 4).

  Patent Document 5 discloses an example in which at least one selected from 5-phenyltropolone, 5-cyanotropolone, and 2-amino-5-phenyltropolone is irradiated with ultraviolet rays and used as an information recording material.

Patent Document 6 discloses a technique for producing a useful photobase generator by irradiating aminotropone with ultraviolet rays to express basicity.
Japanese Patent Laid-Open No. 10-77264 JP 2005-264156 A Japanese Patent Laid-Open No. 2003-212856 Japanese Patent Publication No. 48-818 Japanese Patent Publication No.46-2574 International Publication No. 2008/072651 UV / EB Curing Technology III (1997, CMC Publishing), P78

  However, in the techniques described in Patent Document 1 and Non-Patent Document 1, since carbon dioxide gas is produced as a by-product with exposure, bubbles are generated in the cured product, which is a serious drawback in fine processing and the like. Moreover, in the said technique, since unnecessary by-products, such as an aldehyde, generate | occur | produce, the performance of hardened | cured materials, such as heat resistance and adhesiveness, will fall. Further, in the techniques described in Patent Documents 2 and 3, unnecessary substances are by-produced, so that the performance of the cured product such as heat resistance and adhesiveness is deteriorated. And all the photobase generators used by the said technique contain an ionic component.

  That is, with the conventional resin photocuring techniques including those described above, a photobase generator that exhibits basicity while sufficiently suppressing the generation of unnecessary by-products such as gas and water due to exposure is used. It is difficult. Moreover, although the photobase generator disclosed in Patent Document 6 is a technique that can solve these problems, it is desired to provide a more excellent technique.

  Therefore, the present invention has been made in view of the above circumstances. For example, a suitable photobase generator and a photocurable resin composition that can be used for photocuring of an anion curable resin such as an epoxy resin or a polyimide resin. The purpose is to provide.

  As a result of diligent investigations to solve the above problems, the present inventor can use an aminotropone derivative having a specific substituent constant of a specific numerical value as an excellent photobase generator, and a photocurable resin composition using it can also be used. It has been found useful, and the present invention has been completed.

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、アルキル基、アルケニル基、シクロアルキル基、アラルキル基又はアリール基を表し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、カルボキシル基、アルコキシカルボニル基、シアノ基、ホルミル基、アシル基、ニトロ基、ニトロソ基、アルキル基、アルケニル基、シクロアルキル基、アラルキル基、アリール基、ヒドロキシ基、メルカプト基、アルキルスルファニル基、アルコキシ基、ハロゲン原子又はアミノ基を表す。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６及びＲ_７は、それらのうち少なくとも２つが互いに結合し飽和環又は不飽和環を形成していてもよく、それぞれ独立に式（１）又は（２）で表される誘導体からなる基であって１つの水素原子が脱離した１価の基を置換基として有していてもよい。Ｚは酸素原子又は硫黄原子を表す。）

（式（２）中、Ｒ_１は水素原子、アルキル基、アルケニル基、シクロアルキル基、アラルキル基又はアリール基を表し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７及びＲ_８は、それぞれ独立に、水素原子、カルボキシル基、アルコキシカルボニル基、シアノ基、ホルミル基、アシル基、ニトロ基、ニトロソ基、アルキル基、アルケニル基、シクロアルキル基、アラルキル基、メルカプト基、アルキルスルファニル基、アリール基、ヒドロキシ基、アルコキシ基、ハロゲン原子、アミノ基を表す。
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７及びＲ_８は、それらのうち少なくとも２つが互いに結合し飽和環又は不飽和環を形成していてもよく、それぞれ独立に式（１）又は（２）で表される誘導体からなる基であって１つの水素原子が脱離した１価の基を置換基として有していてもよい。）
［２］上記２−アミノトロポン誘導体は２級アミンである、［１］の光塩基発生剤。
［３］上記２−アミノトロポン誘導体のＲ_１がメチル基でＲ_２が水素原子を表すか、又はＲ_１が水素原子でＲ_２がメチル基を表す、［１］又は［２］の光塩基発生剤。
［４］上記２−アミノトロポン誘導体はＮ−メチル−２−アミノトロポン、Ｎ−メチル−２−アミノ−３，５，７−トリホルミルトロポン、Ｎ−メチル−２−アミノ−３，７−ジホルミルトロポン、Ｎ−メチル−２−アミノ−３，７−ジホルミルトロポン、Ｎ−メチル−２−アミノ−メチルアセテートトロポン、Ｎ−メチル−２−アミノ−４−イソプロピル−７−ホルミルトロポン及びＮ−メチル−７−アミノ−３−イソプロピル−６−ホルミルトロポンからなる群より選ばれた少なくとも１種の化合物である、［１］〜［３］のいずれか一つの光塩基発生剤。
［５］上記２−アミノトロポン誘導体は３級アミンである、［１］の光塩基発生剤。
［６］上記２−アミノトロポン誘導体のＲ_１及びＲ_２がそれぞれメチル基を表す、［５］の光塩基発生剤。
［７］上記２−アミノトロポン誘導体はＮ，Ｎ’−ジメチル−２−アミノトロポン又はＮ，Ｎ’−ジメチル−２−アミノ−７−アセトキシトロポンの少なくともいずれかの化合物である、[１]、[５]及び［６］のいずれか一つの記載の光塩基発生剤。
［８］上記２−アミノトロポン誘導体の０．０４ｍＭシクロヘキサン溶液に対して窒素雰囲気下で紫外線（３６５ｎｍ）を３５ｍＷ／ｃｍ^２の強度で照射して測定される半減期が３．０秒以下である、［１］〜［７］のいずれか一つの光塩基発生剤。
［９］［１］〜［６］のいずれか一つの光塩基発生剤と、アニオン硬化型樹脂と、を少なくとも含有する光硬化型樹脂組成物。
［１０］アニオン硬化型樹脂１００質量部に対して、上記光塩基発生剤を０．００１〜１００質量部含有する［９］の光硬化型樹脂組成物。
［１１］上記アニオン硬化型樹脂はビスフェノールＡ型エポキシ樹脂である［９］又は［１０］の光硬化型樹脂組成物。
［１２］ポリチオールを更に含有する［９］〜［１１］のいずれか一つの光硬化型樹脂組成物。 The present invention provides the following.
The photobase generator which contains the 2-aminotropone derivative represented by Formula (1) or (2), and whose sum total of the substituent constant of the containing substituent is a value exceeding 0.

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R ₃ , R ₄ , R ₅ , R ₆ and R ₇₎ Each independently represents a hydrogen atom, carboxyl group, alkoxycarbonyl group, cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group, hydroxy group, Represents a mercapto group, an alkylsulfanyl group, an alkoxy group, a halogen atom or an amino group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are saturated when at least two of them are bonded to each other. A hydrogen atom, which may form a ring or an unsaturated ring, each independently a group consisting of a derivative represented by the formula (1) or (2), (A monovalent group from which an atom is eliminated may be substituted. Z represents an oxygen atom or a sulfur atom.)

(In the formula (2), _{R 1} represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl _{group, R 3, R 4, R} 5, R 6, R 7 and _{R 8,} Each independently a hydrogen atom, carboxyl group, alkoxycarbonyl group, cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, mercapto group, alkylsulfanyl group, aryl Represents a group, a hydroxy group, an alkoxy group, a halogen atom, or an amino group.
At _{least two of} R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be bonded to each other to form a saturated ring or an unsaturated ring, each independently. May be a group consisting of a derivative represented by the formula (1) or (2) and having a monovalent group from which one hydrogen atom is eliminated as a substituent. )
[2] The photobase generator according to [1], wherein the 2-aminotropone derivative is a secondary amine.
[3] The photobase generation of [1] or [2], wherein R _{1 of the} 2-aminotropone derivative represents a methyl group and R ₂ represents a hydrogen atom, or R ₁ represents a hydrogen atom and R ₂ represents a methyl group Agent.
[4] The 2-aminotropone derivative is N-methyl-2-aminotropone, N-methyl-2-amino-3,5,7-triformyltropone, N-methyl-2-amino-3,7-diformyl. Tropon, N-methyl-2-amino-3,7-diformyl tropone, N-methyl-2-amino-methyl acetate tropone, N-methyl-2-amino-4-isopropyl-7-formyl tropone And a photobase generator according to any one of [1] to [3], which is at least one compound selected from the group consisting of N-methyl-7-amino-3-isopropyl-6-formyltropone.
[5] The photobase generator according to [1], wherein the 2-aminotropone derivative is a tertiary amine.
[6] The photobase generator of [5], wherein R ₁ and R ₂ of the 2-aminotropone derivative each represent a methyl group.
[7] The 2-aminotropone derivative is at least one compound of N, N′-dimethyl-2-aminotropone or N, N′-dimethyl-2-amino-7-acetoxytropone, [1], [1] [5] The photobase generator according to any one of [6].
[8] The half-life measured by irradiating a 0.04 mM cyclohexane solution of the 2-aminotropone derivative with ultraviolet light (365 nm) at an intensity of 35 mW / cm ^{2 in} a nitrogen atmosphere is 3.0 seconds or less. The photobase generator according to any one of [1] to [7].
[9] A photocurable resin composition comprising at least one photobase generator according to any one of [1] to [6] and an anion curable resin.
[10] The photocurable resin composition according to [9], containing 0.001 to 100 parts by mass of the photobase generator with respect to 100 parts by mass of the anion curable resin.
[11] The photocurable resin composition according to [9] or [10], wherein the anion curable resin is a bisphenol A epoxy resin.
[12] The photocurable resin composition according to any one of [9] to [11], further containing a polythiol.

  According to the present invention, for example, an anion curable resin is cured by light irradiation so that basicity can be expressed or increased while sufficiently suppressing generation of unnecessary by-products such as gas and water in performing light irradiation. A photobase generator suitable for the above can be provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. Note that the present embodiment is not construed as being limited to the following, and can be implemented with appropriate modifications within the scope of the gist.

  In the present specification, the “photobase generator” means a compound that expresses or increases basicity upon irradiation with light. Further, “basic” means a property of curing a resin that is cured by a base. Whether or not the resin has been cured can be confirmed by, for example, increasing the degree of polymerization, increasing the degree of crosslinking, and decreasing the solubility in a specific liquid (for example, an alkaline aqueous solution or an organic solvent).

  The 2-aminotropone derivative used in the present embodiment refers to at least one compound represented by the following formula (1) or (2).

In Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, or an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group, and an isopropyl group is preferable. Examples of the alkenyl group include a propenyl group, a butenyl group, and an isobutenyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aralkyl group include a benzyl group. As the aryl group, a phenyl group is preferable.
The case where both R ₁ and R ₂ are hydrogen atoms is defined as a primary amine 2-aminotropone derivative.
A case where any _one of R ₁ and R ₂ is a hydrogen atom is defined as a 2-aminotropone derivative of a secondary amine. Of the secondary aminotropone derivatives, N-methyl-2-aminotropone derivatives are preferable from the viewpoint of curing performance.
The case where both R ₁ and R ₂ are alkyl groups is defined as a tertiary amine 2-aminotropone derivative. Of the 2-aminotropone derivatives of tertiary amines, N, N′-dimethyl-2-aminotropone derivatives are preferable from the viewpoint of curing performance. Generally, more excellent curing performance can be obtained by using R ₁ and R ₂ as substituents which are not bulky.
R _{3 to} R ₇ are each independently a hydrogen atom, carboxyl group, alkoxycarbonyl group, cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, hydroxy group Represents a group, a mercapto group, an alkylsulfanyl group, an aryl group, an alkoxy group, a halogen atom or an amino group.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarboxyl group, and a hydroxyethoxycarbonyl group, and a methoxycarbonyl group is preferable.
As the acyl group, an acetyl group is preferable.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a propenyl group, a butyl group, an isobutyl group, a tert-butyl group, a butenyl group, an isobutenyl group, a benzyl group, and a cyclohexyl group. An isopropyl group is preferred.
Examples of the alkenyl group include a propenyl group, a butenyl group, and an isobutenyl group.
Examples of the cycloalkyl group include a cyclohexyl group.
Examples of the aralkyl group include a benzyl group.
Examples of the alkylsulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a 1-methylsulfide-methyl group, a 2-methylsulfide-ethyl group, and a 3-methylsulfide-propyl group.
The aryl group is preferably a phenyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group, and a methoxy group is preferable.
As the halogen atom, chlorine or bromine is preferable.
As amino group, in addition to unsubstituted amino group, mono-substituted amino group includes methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, cyclohexylamino group, benzylamino group Group, phenylamino group and the like, and methylamino group is preferable.
Examples of the di-substituted amino group include dimethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dicyclohexylamino group, dibenzylamino group, diphenylamino group, pyrrolidino group, piperidino group and morpholino group. And a dimethylamino group is preferred.
R _{1 to} R ₇ are bonded to each other to form a saturated ring or an unsaturated ring such as a pyrazole ring, an imidazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, or a tetrazole ring. You may do it. R _{1 to} R ₇ are groups composed of derivatives represented by the formula (1) or the formula (2), and may have a monovalent group from which one hydrogen atom is eliminated as a substituent. For _example, R 1 to R ₇ may be bonded to the molecule represented in Formula (1) and / or formula (2). Thus, the compound represented by Formula (1) may have a structure having two or more 2-aminotropone structures in one molecule.
Z represents an oxygen atom or a sulfur atom. From the viewpoint of high stability during storage, Z is preferably an oxygen atom.

In the formula (2), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group. R _{3 to} R ₈ are each independently a hydrogen atom, carboxyl group, alkoxycarbonyl group, cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, mercapto Represents a group, an alkylsulfanyl group, an aryl group, a hydroxy group, an alkoxy group, a halogen atom or an amino group.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarboxyl group, and a hydroxyethoxycarbonyl group, and a methoxycarbonyl group is preferable.
As the acyl group, an acetyl group is preferable.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a propenyl group, a butyl group, an isobutyl group, a tert-butyl group, a butenyl group, an isobutenyl group, a benzyl group, and a cyclohexyl group. An isopropyl group is preferred.
Examples of the alkenyl group include a propenyl group, a butenyl group, and an isobutenyl group.
Examples of the cycloalkyl group include a cyclohexyl group.
Examples of the aralkyl group include a benzyl group.
Examples of the alkylsulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a 2-methylsulfide-ethyl group, and a 3-methylsulfide-propyl group.
As the aryl group, a phenyl group is preferable.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group, and a methoxy group is preferable.
As the halogen atom, chlorine or bromine is preferable.
As amino group, in addition to unsubstituted amino group, mono-substituted amino group includes methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, cyclohexylamino group, benzylamino group Group and phenylamino group, and methylamino group is preferable.
Examples of the di-substituted amino group include dimethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dicyclohexylamino group, dibenzylamino group, diphenylamino group, pyrrolidino group, piperidino group and morpholino group. And a dimethylamino group is preferred.
R _{1 to} R ₈ may be bonded to each other to form a saturated or unsaturated ring, or may form an azole ring such as an imidazole ring, an oxazole ring, a thiazole ring, a triazole ring, or a tetrazole ring.
R _{1 to} R ₇ are groups composed of derivatives represented by the formula (1) or the formula (2), and may have a monovalent group from which one hydrogen atom is eliminated as a substituent. For example, R _{1 to} R ₇ may be bonded to a molecule represented by formula (1) and / or formula (2). Thus, the compound represented by Formula (2) also includes a structure having two or more 2-aminotropone structures in one molecule.

In the formula (1), when R ₂ is a hydrogen atom, the structures of the formula (1) and the formula (2) are in a tautomeric relationship (see the following formula (4)). It is.

  The photobase generator according to this embodiment can express basicity by utilizing a seven-membered ring intramolecular photomolecular cyclization reaction. For example, basicity is expressed by cleaving the conjugated system spanning the entire seven-membered ring by the photomolecular cyclization reaction represented by the following formulas (5) and (6) and increasing the electron density on the nitrogen atom Can be made.

  Regarding the fact that a seven-membered ring causes such an intramolecular cyclization reaction, see, for example, O, L, Chapman, Advances in Photochemistry, Vol. 1, p. 323 (1963), etc., and similar reactions have been observed in various molecules regardless of the type of substituent.

The substituent constant used in the present embodiment is the sum of σ _p determined for each substituent present in the seven-membered ring compound. For example, in the compound of the formula (1), it is the sum of σ _p of R _{3 to} R ₇ . In the description of the formula (4), the 2-aminotropone derivative that is a secondary amine is equivalent to the compound (1) because the compound (1) and the compound (2) are equivalent. The aminotropone derivative is not in the form of compound (2).
Then, σ _p is defined by the following equation (7), where K is the dissociation constant K ₀ of the aqueous benzoic acid solution at 25 ° C. and K is the dissociation constant of the para-substituted benzoic acid in the Hammett rule.

  An example of substituent constants that can be used in the present embodiment is shown in Table 1.

  For substituent constants not listed in Table 1, see L.L. P. It can be obtained by measurement according to Hammett, “PHYSICAL ORGANIC CHEMISTRY”, McGraw-Hill, New York (1940).

In addition, the photobase generator of this embodiment has a half-life measured by irradiating ultraviolet light (365 nm) with an intensity of 35 mW / cm ^{2 in} a nitrogen atmosphere to a 0.04 mM cyclohexane solution of a 2-aminotropone derivative. Is preferably less than 3.3 seconds. By using a 2-aminotropone derivative having a substituent constant larger than 0 and a short half-life, a base can be generated efficiently. By using this photobase generator, the curing rate of the photocurable resin can be further increased.

The measurement of the half-life in this embodiment is performed as follows. A 0.04 mM cyclohexane solution of the compound to be measured is irradiated with ultraviolet rays (365 nm) at an intensity of 35 mW / cm ² under a nitrogen atmosphere. The time until the concentration of this compound is halved is measured and defined as the half-life. The measurement can be performed using an ultraviolet-visible spectrophotometer (for example, “V-550” manufactured by JASCO Corporation).

  As a result of intensive studies on photobase generators suitable for photocuring of anion curable resins such as epoxy resins and polyimide resins, the present inventors have found that the substituent constant of the compound is preferably a value exceeding 0. It was. When the substituent constant exceeds 0, basic latent can be achieved. Further, since the photointramolecular cyclization reaction of the photobase generator is fast, less ultraviolet irradiation energy is required to develop basicity. As a result, the photocurable resin composition can be efficiently cured. This substituent constant should just exceed 0, Preferably it is 0.03 or more, More preferably, it is 0.05 or more.

  The photobase generator of this embodiment does not contain an ionic component when unexposed, and can express basicity without by-product such as gas during exposure. And the photocurable resin composition of this embodiment can be used also as resin for electronic materials in which insulation reliability, heat resistance, fine workability, etc. are requested | required severely. In particular, it can be suitably used for photocuring an anion curable resin such as an epoxy resin or a polyimide resin.

  The anion curable resin that can be used in the photocurable resin composition according to the present embodiment is not particularly limited as long as it is a resin curable with a base. Examples of such a resin include an epoxy resin, a polyimide precursor, and a compound having an isocyanate group.

  Examples of the epoxy resin include bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, and cresol novolac type, and bisphenol A type phenol resin is preferable from the viewpoint of curing performance.

  Known epoxy resins can be used, glycidyl ethers of dihydric phenols, polyglycidyl ethers of polyhydric phenols having 3 to 6 or more hydroxy groups, diglycidyl of aliphatic dihydric alcohols. Glycidyl ether type epoxy resins such as ethers, polyglycidyl ethers of aliphatic polyhydric alcohols having 3 to 6 or more hydroxy groups, glycidyl ester type epoxy resins, glycidyl esters of aliphatic or alicyclic polycarboxylic acids , Glycidyl amines of aromatic amines having active hydrogen atoms, glycidyl amines of alicyclic amines having active hydrogen atoms, glycidyl amines of heterocyclic amines having active hydrogen atoms, chain aliphatic epoxides, alicyclic rings Formula epoxide etc.

  Among these, glycidyl ethers of dihydric phenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin di Glycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4′-dihydroxyphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9 , 9'-bis (4-hydroxyphenyl) fluorenediglycidyl ether, bisphenol Such as 2 moles of diglycidyl ether resulting from the reaction of 3 moles of epichlorohydrin and the like.

  Examples of polyglycidyl ethers of polyhydric phenols having 3 to 6 or more hydroxy groups include pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltri Glycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether, 4,4′-oxybis (1,4- Phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (di Droxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolac resin, glycidyl ether of limonene phenol novolac resin, polyglycidyl ether of polyphenol obtained by condensation reaction of phenol with glycoxal, glutaraldehyde or formaldehyde, resorcin and acetone And polyglycidyl ether of polyphenol obtained by a condensation reaction with

  Diglycidyl ethers of aliphatic dihydric alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Examples thereof include glycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide (ethylene oxide or propylene oxide) adduct, and the like.

  Examples of polyglycidyl ethers of aliphatic polyhydric alcohols having 3 to 6 or more hydroxy groups include, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, poly Examples thereof include glycerol polyglycidyl ether.

  Examples of the glycidyl ester type epoxy resin include glycidyl esters of aromatic polycarboxylic acids such as diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and triglycidyl trimellitic acid. In addition, as the glycidyl ester of the aliphatic or alicyclic polycarboxylic acid, the aromatic nucleus hydrogenated product of diglycidyl ester of diglycidyl ester, diglycidyl oxalate, diglycidyl malate, diglycidyl Examples thereof include succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, (co) polymer of glycidyl (meth) acrylate, tricarbyl acid triglycidyl ester, and the like.

  Examples of glycidylamines of aromatic amines having an active hydrogen atom include N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl. Examples thereof include diaminodiphenyl sulfone, N, N, N ′, N′-tetraglycidyl diethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like. Examples of glycidylamines of alicyclic amines having an active hydrogen atom include hydrogenated products of N, N, N ′, N′-tetraglycidylxylylenediamine. Examples of glycidylamines of heterocyclic amines having an active hydrogen atom include trisglycidylmelamine.

  Examples of chain aliphatic epoxides include epoxidized butadiene and epoxidized soybean oil. Examples of alicyclic epoxides include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, and 3,4-epoxy-6. -Methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) ) Butylamine.

  The epoxy resin which concerns on this embodiment is used individually by 1 type or in combination of 2 or more types. From the viewpoint of the performance and availability of the cured product, the epoxy resin is preferably a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin, and more preferably a glycidyl ether type epoxy resin.

  When the anion curable resin is an epoxy resin, a curing agent can be blended as necessary. Thereby, the sclerosis | hardenability of a photocurable resin composition further improves. The functional group having reactivity with the epoxy resin is not particularly limited as long as it is a functional group known to react with the epoxy resin, and is carboxyl group, thiol group, phenolic hydroxyl group, primary or secondary aromatic. An amino group etc. are mention | raise | lifted. Among them, a thiol group and / or a phenolic hydroxyl group is preferable from the viewpoint of high reactivity.

  The compound having two or more thiol groups, that is, polythiol is not particularly limited as long as it is a known compound, and examples thereof include alkylthiol compounds having 1 to 20 carbon atoms and 2 to 6 or more functional groups. Examples of such alkyl thiol compounds include 1,4-butanedithiol and 1,8-octanedithiol. Other compounds having thiol groups include thiols obtained by the reaction of polyepoxide and hydrogen sulfide, mercaptocarboxylic acids having 2 to 20 carbon atoms and 2 to 3 or more functional groups (for example, mercaptoacetic acid, mercaptopropion). Acid, mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid) and an esterified product of a polyol having 2 to 30 carbon atoms and 2 to 6 functional groups. Among them, an esterified product of mercaptocarboxylic acid and the above polyol is preferable from the viewpoint of the performance of the cured product and availability. In particular, when the anion curable resin is bisphenol A type, it is preferable to use polythiol.

  The compound having a phenolic hydroxyl group is not particularly limited as long as it is a known compound, and examples thereof include phenolic resins such as novolac resins and resol resins. Among them, a novolak resin is more preferable from the viewpoint of the performance of the cured product. Examples of novolak resins include phenol novolac resins and cresol novolac resins. Among them, a cresol novolac resin is more preferable from the viewpoint of the performance of the cured product.

  The amount of the curing agent to be added is not limited, but in view of curing performance, it is blended in a weight ratio with the anion curable resin and anionic curable resin: curing agent = 100: 0 to 10:90. can do. Preferably, the range is anion curable resin: curing agent = 100: 0 to 30:70, and more preferably an anion curable resin: curing agent = 100: 0 to 50:50.

  The polyimide precursor may be a single material or a mixture of two or more separately synthesized precursors, and polyamic acid is preferably used. A polyamic acid can be obtained by mixing an acid dianhydride and a diamine in a solution. Therefore, the polyamic acid can be synthesized by a one-step reaction. The polyimide precursor may be a single type or a mixture of two or more types of separately synthesized precursors, a system that forms a polyimide by ring closure of polyamic acid, or a system that converts polyisoimide to polyimide. Etc.

  When the heat resistance and dimensional stability requirements of the finally obtained polyimide are severe, the polyimide precursor has a portion derived from dianhydride having an aromatic structure and a portion derived from diamine. Is preferably a wholly aromatic polyimide precursor containing an aromatic structure. Therefore, the structure of the diamine-derived portion is preferably a structure derived from an aromatic diamine.

  Here, the wholly aromatic polyimide precursor means a polyimide precursor obtained by copolymerization of an aromatic acid component and an aromatic amine component, or polymerization of an aromatic acid / amino component, and a derivative thereof. The aromatic acid component means a compound in which all four acid groups forming the polyimide skeleton are substituted on the aromatic ring, and the aromatic amine component means two amino groups forming the polyimide skeleton. Both refer to compounds that are substituted on the aromatic ring. Further, the aromatic acid / amino component is a compound in which both an acid group and an amino group forming a polyimide skeleton are substituted on an aromatic ring. However, as is clear from specific examples of the raw materials described later, all of the acid groups or amino groups may be present on the same aromatic ring or may be present on different aromatic rings.

  A conventionally well-known method can be applied as a manufacturing method of a polyimide precursor. For example, a method of synthesizing a polyamic acid as a precursor from an acid dianhydride and a diamine may be used. Alternatively, a polyimide precursor can be obtained by further reacting a diamino compound or a derivative thereof with a carboxylic acid such as an ester acid or an amic acid monomer obtained by reacting an acid dianhydride with a monohydric alcohol, an amino compound or an epoxy compound. It may be a method of synthesizing the body. However, the manufacturing method of a polyimide precursor is not limited to these.

  Examples of the acid dianhydride applicable to the production of the polyimide precursor include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic dianhydride. Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 , 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxy) Phenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoro Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4- Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) Phenoxy] phenyl} propane Anhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} Ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl Anhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2- Dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) ) Phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafulpropane Anhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-propane dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4 Benzenetetracarboxylic dianhydride, 3, , 9,10 Bae Li Ren dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride and the like. These may be used alone or in combination of two or more.

  Particularly preferred tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra. Carboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  When an acid dianhydride into which fluorine is introduced or an acid dianhydride having an alicyclic skeleton is used in combination with the above-described one as the acid dianhydride, the transparency of the polyimide precursor is improved.

  Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. When used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small.

  The diamine which is an amine component is also used individually by 1 type or in mixture of 2 or more types.

  The amine component diamine is not particularly limited, and examples thereof include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -Diaminodiph Nylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2 -Di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1 -Phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis ( 3-Aminophenoxy) benzene, 1,3 Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis ( 4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dito Trifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2 , 6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-amino) Phenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4- Minophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3- Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1 , 4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- ( 4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4- Aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α- Dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophen) Xyl) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6, 6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′ , 3′-tetramethyl-1,1′-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω- Bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [2- (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- ( 3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether , Ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopen 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4 -Di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] Heptane and the like.

  One or more of the hydrogen atoms on the aromatic ring of the diamine described above are selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. Diamines substituted with substituents may be used.

  Furthermore, depending on the purpose, one or more selected from the group consisting of an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, and an isopropenyl group that serve as a crosslinking point. May be introduced as a substituent on some or all of the hydrogen atoms on the aromatic ring of the diamine.

  The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient. Examples of the rigid diamine include diamines in which two amino groups are bonded to the same aromatic ring. Specific examples include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1 , 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene.

  Furthermore, a diamine in which two or more aromatic rings are bonded by a single bond and two or more amino groups are bonded to separate aromatic rings directly or as part of a substituent may be used. An example of such a diamine is benzidine.

  On the other hand, when a diamine having a siloxane skeleton, such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane, is used as the diamine, the elastic modulus of the finally obtained polyimide is lowered and the glass transition temperature is lowered. be able to.

  Here, the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance. However, diamines other than aromatics such as aliphatic diamines and siloxane diamines may be used within a range not exceeding 60 mol%, preferably 40 mol% of the total diamine, depending on the desired physical properties.

  The compound having an isocyanate group is not particularly limited as long as it has two or more isocyanate groups in the molecule, and a known compound is employed. Examples of such compounds include low molecular weight compounds such as p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, and hexamethylene diisocyanate. Other specific examples include, as such compounds, polymers having a weight average molecular weight of 3000 or more and having an isocyanate group in the side chain or terminal.

  When the above-mentioned compound having an isocyanate group is used as the anion curable resin, it is usually used in combination with a compound having two or more hydroxy groups in the molecule. It does not specifically limit as a compound which has the hydroxyl group, A well-known thing is employ | adopted. Specific examples thereof include low molecular compounds such as ethylene glycol, propylene glycol, glycerin, diglycerin and pentaerythritol. Other specific examples include polymers having a weight average molecular weight of 3000 or more and having a hydroxy group in the side chain or terminal. The compound having two or more hydroxy groups in the molecule is 0.5 / 1. In terms of (total amount of hydroxy groups) / (total amount of isocyanate groups) (equivalent ratio) with respect to the compound having isocyanate groups. It is preferably used in an amount such that the ratio is 5 to 1.5 / 0.5, and is preferably used in such an amount that the ratio is 0.8 / 1.2 to 1.2 / 0.8. More preferred. When the photocurable resin composition contains the above-described compound in such a ratio, the curability tends to be further improved.

  The amount of the photobase generator when the photobase generator is blended with the anion curable resin to form a photocurable resin composition is not limited, but is preferably 0 with respect to 100 parts by mass of the anion curable resin. 0.001 to 100 parts by mass, preferably 0.005 to 80 parts by mass, and more preferably 0.01 to 50 parts by mass. By setting it to 0.001 part by mass or more, a sufficiently practical curing rate can be obtained. By setting it to 100 parts by mass or less, excellent physical properties of the cured product can be obtained.

  In addition, an organic solvent, an inorganic filler, a colorant, a polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, an adhesion imparting agent, a photo radical initiator, etc. are used alone in the photocurable resin composition of the present embodiment. Alternatively, adding two or more types in combination does not impair the intention of the present embodiment, and can be added as necessary.

  The organic solvent is not particularly limited. For example, ethers such as diethyl ether, tetrahydrofuran and dioxane; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether (so-called cellosolves) Ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; esters such as ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate; methanol, ethanol, isopropanol, butanol, cyclohexanol, Alcohols such as ethylene glycol and glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropro Halogenated hydrocarbons such as chlorobenzene, amides such as N, N-dimethylformamide and N, N-dimethylacetamide; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; dimethyl sulfoxide and the like Examples thereof include sulfoxides; linear or cyclic saturated hydrocarbons such as hexane, cyclohexane and heptane; and other organic polar solvents. Furthermore, examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene, and other organic nonpolar solvents. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  The inorganic filler is not particularly limited, and examples thereof include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, aluminum oxide, aluminum hydroxide, and mica. . By using the inorganic filler, various physical properties such as adhesion between the cured body and the substrate and hardness of the cured body can be improved.

  The colorant is not particularly limited, and examples thereof include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

  The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine.

  The thickener is not particularly limited, and examples include asbestos, olben, benton, and montmorillonite.

  Although it does not specifically limit as an antifoamer, A silicone type, a fluorine type, a polymeric type etc. are mention | raise | lifted.

  Although it does not specifically limit as a leveling agent, Organic modified polysiloxane, modified polyacrylate, etc. are mention | raise | lifted.

  The adhesiveness imparting agent is not particularly limited, and examples thereof include imidazole-based, thiazole-based, triazole-based, and silane coupling agents.

  Although it does not specifically limit as a radical photoinitiator, A benzophenone derivative, an acetophenone derivative, etc. are mention | raise | lifted.

  The photocurable resin composition of the present embodiment can be cured by light irradiation. At that time, only light irradiation may be performed, light irradiation and heating may be performed simultaneously, or heating may be performed after the light irradiation.

The light source and conditions for light irradiation can be selected as appropriate, but it is preferable to use irradiation light in the wavelength region of 150 to 750 nm. More specifically, it is preferable to perform light irradiation at a dose of 0.01 to 100 J / cm ² using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp and / or a metal hydride lamp. Thereby, a photocurable resin composition can be hardened efficiently. It is more preferable to perform light irradiation at an irradiation amount of 0.05 to 20 J / cm ² using irradiation light in a wavelength region of 200 to 400 nm.
The atmosphere for light irradiation may be in air or in an inert gas, but is preferably in an inert gas, more preferably in a nitrogen gas atmosphere.

The heating temperature in the case of heating is not particularly limited as long as it is a temperature below the decomposition point of the anion curable resin, but is preferably 30 to 400 ° C, and more preferably 50 to 300 ° C.
The heating time for heating is not particularly limited, but is preferably 1 second to 3 hours, more preferably 30 seconds to 1 hour, from the viewpoint of sufficient curing. The atmosphere for heating is not limited, and can be performed in air or in an inert gas, for example.

Hereinafter, the present embodiment will be described in more detail by way of examples. However, the present embodiment is not construed as being limited to these examples.
First, the photocurable resin composition which mix | blended the photobase generator on various conditions was manufactured. And the physical property was evaluated by performing light irradiation and heating with respect to these.

(Production Example 1)
[Production of photobase generator 1]
N-methyl-2-amino-3,5,7-triformyltropone was synthesized as follows.
1.04 g of tropolone (manufactured by Wako Pure Chemical Industries, Ltd.), 2 mL of water, 1.6 mL of 8M KOH, and 13.8 g of 36% formalin aqueous solution were mixed and reacted at 70 ° C. for 10 hours. After completion of the reaction, when the pH of the solution was adjusted to 3 to 4, a cream colored solid was precipitated. This was collected by suction filtration and vacuum-dried to obtain an intermediate (1-1).
200 mg of the intermediate (1-1), 6.3 mL of a 10% trimethylsilyldiazomethane / hexane solution, and 6 mL of a 20% methanol / benzene solution were mixed and reacted at room temperature for 20 hours. After completion of the reaction, the solvent was distilled off to obtain an intermediate (1-2).
Next, 200 mg of the intermediate (1-2), 400 mg of 40% methylamine aqueous solution, and 10 mL of ethanol were mixed, and the reaction was performed in a reflux state for 3 hours. After completion of the reaction, the solvent was distilled off to obtain an intermediate (1-3).
Next, 200 mg of the intermediate (1-3), 3.1 g of MnO ₂ and 4 mL of benzene were mixed and reacted at room temperature for 24 hours. After completion of the reaction, after removal of the solvent by an evaporator, added with methylene chloride 2 mL, disodium ethylenediaminetetraacetate dihydrate _{(EDTA · 2Na · 2H 2 O} ) 1g dissolved aqueous 1N NaOH solution 12mL was. After stirring for 1 hour, the mixture is allowed to stand, phase separation is performed, and the oil phase is recovered. Add 0.5 g of magnesium sulfate to the recovered oil phase and stir for 1 hour. Thereafter, the filtrate was recovered by filtration, and the solvent was removed from the filtrate by an evaporator.
Then, the filtrate from which the solvent was removed was separated and purified on a column to obtain the target N-methyl-2-amino-3,5,7-triformyltropone (141 mg, 0.6 mmol, brown, solid). It was.
[Production of Photocurable Resin Composition 1]
A compound was mixed in the following composition to obtain a photocurable resin composition 1.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
N-methyl-2-amino-3,5,7-triformyltropone (photobase generator 1) 0.12 g
The substituent constant of N-methyl-2-amino-3,5,7-triformyltropone was 0.66.

(Production Example 2)
[Production of photobase generator 2]
Synthesis of N-methyl-2-amino-3,7-diformyltropone was performed as follows.
New Experimental Chemistry Lecture 14 Synthesis and reaction of organic chemistry [II], edited by The Chemical Society of Japan, Maruzen Co., Ltd., p919, 5-aminotropolone was synthesized from tropolone. 5-Chlorotropolone was synthesized from 5-aminotropolone by the method described in New Experimental Chemistry Lecture 14 Organic Chemistry Synthesis and Reaction [II], edited by The Chemical Society of Japan, Maruzen Co., Ltd., p920.
After 900 mg of 5-chlorotropolone and 20 mL of 0.5 M KOH / MeOH solution were mixed and completely homogenized, the solvent was distilled off to obtain a potassium salt of 5-aminotropolone. To this, 50 mL of water was added to 12 g of 36% formalin aqueous solution and reacted at 70 ° C. for 8 hours. After completion of the reaction, 60 g of ammonium chloride and 100 mL of methylene chloride were added to the reaction solution and mixed with stirring. Thereafter, the reaction solution was allowed to stand for phase separation, and the oil phase was recovered. After adding 2 g of magnesium sulfate to the recovered oil phase and stirring for 1 hour, the filtrate was recovered by filtration. The solvent was distilled off from this filtrate to obtain an intermediate (2-1).
Subsequently, 200 mg of the intermediate (2-1), 6.3 mL of a 10% trimethylsilyldiazomethane / hexane solution, and 6 mL of a 20% methanol / benzene solution were mixed and reacted at room temperature for 20 hours. After completion of the reaction, the solvent was distilled off to obtain an intermediate (2-2).
150 mg of intermediate (2-2), 3.2 mL of 8M KOH aqueous solution, and 3 mL of water were added and stirred to dissolve intermediate (2-2). To this solution, 0.38 g of palladium-carbon (Pd-supported 5 wt%) was added. Then, hydrogen gas was put into the reactor and reacted at room temperature and normal pressure for 24 hours to carry out hydrogenation reaction. After completion of the reaction, the filtrate was collected by filtration, and 0.75 mL of 30% hydrochloric acid aqueous solution was added to the filtrate. Subsequently, 100 mL of ethyl acetate was added and this solution mixed with stirring was allowed to stand and phase separation was performed to recover the oil phase. To this oil phase, 2 g of magnesium sulfate was added and stirred for 1 hour, followed by filtration to recover the filtrate. The solvent was distilled off from the obtained filtrate to obtain an intermediate (2-3).
Next, 150 mg of the intermediate (2-3), 300 mg of a 40% methylamine aqueous solution and 10 mL of ethanol were mixed and reacted for 3 hours under reflux. After completion of the reaction, the solvent was distilled off to obtain an intermediate (2-4).
Next, 150 mg of the intermediate (2-4), 2.3 g of MnO ₂ and 3 mL of benzene were mixed and reacted at room temperature for 24 hours. After completion of the reaction, the solvent is removed by an evaporator, and then 2 mL of methylene chloride and 8 mL of 1N NaOH aqueous solution in which 0.8 g of disodium ethylenediaminetetraacetate (EDTA · 2Na · 2H ₂ O) is dissolved are added. . After stirring for 1 hour, the mixture is allowed to stand, phase separation is performed, and the oil phase is recovered. Add 0.5 g of magnesium sulfate to the recovered oil phase and stir for 1 hour. Thereafter, the filtrate was recovered by filtration, and the solvent was removed from the filtrate by an evaporator.
Then, the filtrate from which the solvent was removed was separated and purified by a column to obtain N-methyl-2-amino-3,7-diformyltropone (122 mg, 0.6 mmol, brown, solid) as a target product.
[Production of Photocurable Resin Composition 2]
A compound was mixed in the following composition to obtain a photocurable resin composition 2.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
N-methyl-2-amino-3,7-diformyltropone (photobase generator 2) 0.12 g
The substituent constant of N-methyl-2-amino-3,7-diformyltropone was 0.44.

(Production Example 3)
[Production of photobase generator 3]
N-methyl-2-amino-methyl acetate tropone was synthesized as follows.
First, Tetrahedron, Vol. 31, p1483-1489, (1975), N-methyl-2-amino-5-cyanotropone was synthesized from 5-cyanotropone.
Subsequently, Tetrahedron, Vol. 31, p1483-1489, (1975), 2-methyl-5-carboxytropone was synthesized from N-methyl-2-amino-5-cyanotropone.
Furthermore, Tetrahedron, Vol. 31, the target N-methyl-2-amino-5-methyl acetate tropone was synthesized from 2-methyl-5-carboxyl tropone by the method described in (1975).
[Production of Photocurable Resin Composition 3]
A compound was mixed in the following composition to obtain a photocurable resin composition 3.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
N-methyl-2-amino-5-methyl acetate tropone (photobase generator 3) 0.12 g
The substituent constant of N-methyl-2-amino-5-methyl acetate tropone was 0.44.

(Production Example 4)
[Production of photobase generator 4]
Synthesis of methylamino-formyl-isopropyltropone (mixture of N-methyl-2-amino-4-isopropyl-7-formyltropone and N-methyl-7-amino-3-isopropyl-6-formyltropone) It carried out as follows.
5.0 g of 4-isopropyl tropolone (manufactured by Asahi Kasei Finechem Co., Ltd., hinokitiol) and 4.9 mL of 8M KOH aqueous solution were mixed and dissolved. Water 5mL and 36% formalin aqueous solution 3.5g were added to this, and it stirred at 70 degreeC, and made it react for 24 hours. After completion of the reaction, 30 mL of 30% aqueous hydrochloric acid and 70 mL of ethyl acetate were added and mixed with stirring. The reaction solution was allowed to stand and phase-separated to recover an oil phase. 2 g of magnesium sulfate was added to the recovered oil phase, stirred for 1 hour, and filtered to recover the filtrate. The solvent was distilled off from the filtrate, and the reaction product was recovered to obtain an intermediate (3-1).
2.0 g of the intermediate (3-1), 20.6 mL of a 10% trimethylsilyldiazomethane / hexane solution, and 30 mL of a 20% MeOH / benzene solution were mixed and stirred, and reacted at room temperature for 16.5 hours. After completion of the reaction, the solvent was distilled off to obtain an intermediate (3-2).
Intermediate (3-2) 400 mg, 40% methylamine aqueous solution 745 mg, and ethanol 10 mL were mixed and reacted for 3 hours under reflux. After completion of the reaction, the solvent was distilled off to obtain an intermediate (3-3).
Intermediate (3-3) 310 mg, benzene 6 mL, and MnO ₂ 4.8 g were mixed and reacted at room temperature for 2 hours with stirring. The reaction solution was filtered to obtain a filtrate. The solvent was distilled off from the filtrate to obtain a recovered product. This recovered material was dissolved in 3 mL of methylene chloride, 1.5 g of disodium ethylenediaminetetraacetate (EDTA · 2Na · 2H ₂ O) and 18 mL of 1N NaOH aqueous solution were added, and the mixture was stirred for 1 hour. After stirring, the reaction solution was allowed to stand and phase-separated to recover the oil phase. To this oil phase, 0.5 g of magnesium sulfate was added and stirred for 1 hour. After the reaction solution was collected by filtration, the solvent was distilled off, and the target product methylamino-formyl-isopropyltropone (N-methyl-2-amino-4-isopropyl-7-formyltropone and N- A mixture of methyl-7-amino-3-isopropyl-6-formyltropone) (220 mg, 1.2 mmol, brown, solid) was obtained.
[Production of Photocurable Resin Composition 4]
A compound was mixed in the following composition to obtain a photocurable resin composition 4.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
Methylamino-formyl-isopropyltropone (mixture of N-methyl-2-amino-4-isopropyl-7-formyltropone and N-methyl-7-amino-3-isopropyl-6-formyltropone) (light Base generator 4) 0.12 g
In addition, methylamino-formyl-isopropyltropone (a mixture of N-methyl-2-amino-4-isopropyl-7-formyltropone and N-methyl-7-amino-3-isopropyl-6-formyltropone) The substituent constant was 0.07.

(Production Example 5)
[Production of photobase generator 5]
Synthesis of N, N′-dimethyl-2-amino-7-acetoxytropone was performed as follows.
30 g of tropolone (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 90 g of pyridine. To this, 50.3 g of p-toluenesulfonyl chloride was added and reacted at room temperature for 5 hours. After completion of the reaction, 107 g of 30% hydrochloric acid aqueous solution was added. Subsequently, 100 g of water and 100 mL of diethyl ether were added and mixed with stirring. Thereafter, the reaction solution is allowed to stand for phase separation, and the oil phase is recovered. This oil phase was washed with 100 g of a saturated aqueous sodium hydrogen carbonate solution. Then, this was left still and phase-separated and the oil phase was collect | recovered. 1 g of magnesium sulfate was added to this oil phase and stirred for 1 hour. After stirring, the filtrate was collected by filtration, and then the solvent was distilled off to obtain an intermediate (5-1).
2 g of the intermediate (5-1), 2.0 g of 50% dimethylamine aqueous solution and 60 mL of ethanol were mixed and reacted for 2.5 hours under reflux. After completion of the reaction, the solvent was distilled off, and 100 mL of water, 7 mL of a saturated aqueous sodium bicarbonate solution, and 100 mL of ethyl acetate were added and stirred. Then, it left still and phase-separated and collect | recovered the oil phase. 1 g of magnesium sulfate was added to the recovered oil phase and stirred for 1 hour. Then, it filtered and collect | recovered the filtrate. Then, the solvent was distilled off to obtain N, N′-dimethyl-2-aminotropone.
Subsequently, the target N, N′-dimethyl-2-amide is obtained from N, N′-dimethyl-2-aminotropone by the method described in Chem, Pharm, Bull, 39 (7), P1843-1845 (1991). Amino-7-acetoxytropone was obtained.
[Production of Photocurable Resin Composition 5]
A compound was mixed in the following composition to obtain a photocurable resin composition 5.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.35 g
Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 g
N, N'-dimethyl-2-amino-7-acetoxytropone (photobase generator 5) 0.12 g
Note that the substituent constant of N, N′-dimethyl-2-amino-7-acetoxytropone was 0.5.

(Production Example 6)
[Production of Photocurable Resin Composition 6]
A compound was mixed in the following composition to obtain a photocurable resin composition 6.
・ Bisphenol A type epoxy resin (product name “AER250”, manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
Methylamino-formyl-isopropyltropone (mixture of N-methyl-2-amino-4-isopropyl-7-formyltropone and N-methyl-7-amino-3-isopropyl-6-formyltropone) (light Base generator 4) 0.035 g
In addition, methylamino-formyl-isopropyltropone (a mixture of N-methyl-2-amino-4-isopropyl-7-formyltropone and N-methyl-7-amino-3-isopropyl-6-formyltropone) The substituent constant was 0.07.

(Production Example 7)
[Production of photobase generator 7]
N-methyl-2-aminotropone was synthesized as follows.
7.6 g of Tropolone (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 25 mL of pyridine, 12.5 g of p-toluenesulfonyl chloride was added, and the mixture was stirred at room temperature for 20 hours to be reacted. Thereafter, 200 mL of water was added and sufficiently stirred, followed by suction filtration, washing with water, and drying to obtain tropolone tosylate as a solid. To 1.65 g of the obtained tosylate, 50 mL of ethanol and 1.4 g of a 40 wt% aqueous solution of methylamine were added and heated under reflux for 2 hours. Ethanol was distilled off under reduced pressure, 20 mL of water and 2 mL of saturated aqueous sodium hydrogen carbonate solution were added and stirred, and then extracted twice with 30 mL of diethyl ether. Magnesium sulfate was added to the obtained diethyl ether solution and dried, followed by filtration. Then, diethyl ether was distilled off to obtain N-methyl-2-aminotropone (630 mg, 4.7 mmol, yellow, solid) as a target product.
[Production of Photocurable Resin Composition 7]
A compound was mixed in the following composition to obtain a photocurable resin composition 6.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
・ N-methyl-2-aminotropone (photobase generator 7) 0.076 g
The substituent constant of N-methyl-2-aminotropone was 0.

(Production Example 8)
[Production of photobase generator 8]
Synthesis of methylamino-isopropyltropone was performed as follows.
5.1 g of 4-isopropyl tropolone (manufactured by Asahi Kasei Finechem Co., Ltd., hinokitiol) was dissolved in 12 mL of pyridine, 6.24 g of p-toluenesulfonyl chloride was added, and the mixture was stirred at room temperature for an hour. Subsequently, 80 mL of water was added, 11 mL of concentrated hydrochloric acid was added and the mixture was sufficiently stirred, and then extracted twice with 30 mL of diethyl ether. Magnesium sulfate was added to the obtained diethyl ether solution, dried and filtered, and then diethyl ether was distilled off to obtain 4-isopropyltropolone tosylate.
To 1.9 g of the resulting tosylate, 50 mL of ethanol and 1.4 g of a 40 wt% aqueous solution of methylamine were added and heated to reflux for 2 hours. Ethanol was distilled off under reduced pressure, 20 mL of water and 2 mL of saturated aqueous sodium hydrogen carbonate solution were added and stirred, and then extracted twice with 20 mL / 20 mL of diethyl ether / ethyl acetate. Magnesium sulfate was added to the obtained diethyl ether / ethyl acetate solution, dried and filtered. Diethyl ether / ethyl acetate was distilled off under reduced pressure, and the target product, methylamino-isopropyltropone (2-methylamino-4- A mixture of isopropyl tropone and 2-methylamino-6-isopropyl tropone) (0.98 g, 5.5 mmol, brown, high viscosity liquid) was obtained.
[Production of Photocurable Resin Composition 8]
A compound was mixed in the following composition to obtain a photocurable resin composition 8.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
Methylamino-isopropyl tropone (mixture of N-methyl-2-amino-4-isopropyl tropone and N-methyl-2-amino-6-isopropyl tropone) (photobase generator 8) 0.10 g
The substituent constant of methylamino-isopropyl tropone (a mixture of N-methyl-2-amino-4-isopropyl tropone and N-methyl-2-amino-6-isopropyl tropone) was −0.15. It was.

(Production Example 9)
[Production of photobase generator 9]
Synthesis of N-methyl-2-amino-3,7-dimethyltropone was performed as follows.
50 mg of the intermediate (2-1), 1.6 g of acetic acid, 0.15 g of water, 100 mg of red phosphorus and 100 mg of iodine were mixed and stirred, and reacted at 110 ° C. for 4 hours. Then, 15.7 g of 1N NaOH aqueous solution and 1 g of 0.5N sodium thiosulfate were added to the reaction solution and stirred. Subsequently, 0.1 g of acetic acid and 20 mL of ethyl acetate were added and stirred. Thereafter, the reaction solution was allowed to stand for phase separation, and the oil phase was recovered. After adding 1 g of magnesium sulfate to the oil phase and stirring for 1 hour, the filtrate was collected by filtration. The filtrate was evaporated to recover the reaction product. This was repeated to obtain an intermediate (9-1).
900 mg of the intermediate (9-1) and 18.7 mL of 8M KOH aqueous solution were mixed and dissolved. To this solution was added 2 g of palladium-carbon. Then, hydrogen gas was introduced into the reactor, and a hydrogenation reaction was performed at room temperature and normal pressure for 24 hours. After completion of the reaction, the filtrate was collected by filtration. To this filtrate, 4.5 mL of 30% aqueous hydrochloric acid was added. Subsequently, 200 mL of ethyl acetate was added and mixed with stirring. The reaction solution was allowed to stand for phase separation, and the oil phase was recovered. 2 g of magnesium sulfate was added to the recovered oil phase and stirred for 1 hour, followed by filtration to recover the filtrate. The solvent was distilled off from the filtrate to obtain an intermediate (9-2).
200 mg of the intermediate (9-2), 13 mL of 20% methanol / benzene solution, and 9 mL of 10% trimethylsilyldiazomethane / hexane solution were mixed and stirred, and reacted at room temperature for 48 hours. After completion of the reaction, the solvent was distilled off from the resulting reaction solution to obtain an intermediate (9-3).
Intermediate (9-3) 200 mg, ethanol 18 mL, and 40% methylamine aqueous solution 1.9 g were mixed and reacted for 6 hours under reflux. After completion of the reaction, the solvent was distilled off from the reaction solution to obtain N-methyl-2-amino-3,7-dimethyltropone (218 mg, 1.3 mmol, brown, high viscosity liquid).
[Production of Photocurable Resin Composition 9]
A compound was mixed in the following composition to obtain a photocurable resin composition 9.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
N-methyl-2-amino-3,7-dimethyltropone (photobase generator 9) 0.092 g
The substituent constant of N-methyl-2-amino-3,7-dimethyltropone was -0.34.

(Production Example 10)
[Production of photobase generator 10]
N-methyl-2-amino-7-methoxytropone was synthesized as follows.
Bull. Chem. Soc. Jap. , 51 (8), 2338, (1978), and N-methyl-3-aminotropolone was synthesized from tropolone.
120 mg of N-methyl-3-aminotropone, 10 mL of 10% trimethylsilyldiazomethane / hexane solution, and 20 mL of 20% methanol / benzene solution were mixed and reacted at room temperature for 24 hours. After completion of the reaction, the solvent was distilled off and the reaction product was recovered. This was purified by a column to obtain N-methyl-2-amino-7-methoxytropone (0.1 g, 0.61 mmol, brown, solid) as a target product.
[Production of Photocurable Resin Composition 10]
A compound was mixed in the following composition to obtain a photocurable resin composition 10.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
N-methyl-2-amino-7-methoxytropone (photobase generator 10) 0.093 g
The substituent constant of N-methyl-2-amino-7-methoxytropone was −0.27.

(Production Example 11)
[Production of photobase generator 11]
N, N′-dimethyl-2-aminotropone was synthesized as follows.
2 g of the intermediate (5-1), 2.0 g of 50% dimethylamine aqueous solution and 60 mL of ethanol were mixed and reacted for 2.5 hours under reflux. After completion of the reaction, the solvent was distilled off, and 100 mL of water, 7 mL of a saturated aqueous sodium hydrogen carbonate solution and 100 mL of ethyl acetate were added and stirred. Then, it left still and phase-separated and collect | recovered the oil phase. 1 g of magnesium sulfate was added to the recovered oil phase and stirred for 1 hour. Then, it filtered and collect | recovered the filtrate. The solvent was removed from the filtrate to recover the reaction product. This reaction product was separated and purified by a column to obtain N, N′-dimethyl-2-aminotropone (2.2 g, 14.8 mmol, yellow, solid).
[Production of Photocurable Resin Composition 11]
A compound was mixed in the following composition to obtain a photocurable resin composition 11.
・ Bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 0.70 g
・ Tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g
・ N, N′-dimethyl-2-aminotropone (photobase generator 11) 0.084 g
The substituent constant of N, N′-dimethyl-2-aminotropone was 0.

[Measurement of half-life]
The half-life was measured as an index of the rate of photochemical reaction of each compound.
Each compound was used as a sample as a 0.04 mM solution of cyclohexane. Each sample was fully deoxygenated by nitrogen substitution.
A quartz glass container (1 cm × 1 cm × 5 cm) is filled with 4.5 mL of a sample (0.04 mM cyclohexane solution) and irradiated with ultraviolet light in a nitrogen atmosphere. Ultraviolet rays were irradiated at 365 nm with an intensity of 35 mW / cm ² , and the concentration of the compound was measured from the UV absorption spectrum of the sample. The time when the concentration of this compound reached 0.02 mM was measured, and the time was defined as the half-life (s). An ultraviolet-visible spectrophotometer (manufactured by JASCO, “V-550”) was used for measurement of the UV absorption spectrum.

[Measurement of basic latency]
For the evaluation of the presence or absence of the basic latent of each compound, the curability when heated without UV irradiation and the curability when heated after UV irradiation are evaluated, respectively. It is not cured by heating without irradiation, and it is evaluated that the basic latent has been made when it is heated after being irradiated with ultraviolet rays.
(2) Those that were cured simply by heating without being irradiated with ultraviolet rays were evaluated as having no basic latentity.

Example 1
[When N-methyl-2-amino-3,5,7-triformyltropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 1 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it did not harden even after 30 minutes and remained liquid and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 10 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 7 minutes, it was completely cured and a strong coating film was obtained.
N-methyl-2-amino-3,5,7-triformyltropone in cyclohexane solution (0.04 mM) was irradiated with 365 nm ultraviolet light at an intensity of 35 mW / cm ² and its half-life was measured. As a result, it was 3.02 seconds.

(Example 2)
[When N-methyl-2-amino-3,7-diformyltropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 2 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it did not harden even after 30 minutes and remained liquid and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 9 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 4 minutes, it was completely cured and a strong coating film was obtained.
N-methyl-2-amino-3,7-diformyltropone in cyclohexane solution (0.04 mM) was irradiated with 365 nm ultraviolet light at an intensity of 35 mW / cm ² and its half-life was measured. It was 1.83 seconds.

(Example 3)
[When N-methyl-2-amino-methyl acetate tropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 3 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it did not harden even after 30 minutes and remained liquid and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 9 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 5 minutes, it was completely cured and a strong coating film was obtained.
As a result of measuring the half-life of N-methyl-2-amino-methyl acetate tropone in cyclohexane solution (0.04 mM) by irradiating 365 nm ultraviolet light with an intensity of 35 mW / cm ² , 2.35 seconds Met.

Example 4
[When methylamino-formyl-isopropyltropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 4 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it was not cured even after 60 minutes and remained in a liquid state and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 6 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 7 minutes, it was completely cured and a strong coating film was obtained.
The half-life of the methylamino-formyl-isopropyltropone cyclohexane solution (0.04 mM) irradiated with 365-nm ultraviolet light at an intensity of 35 mW / cm ² was 2.93 seconds.

(Example 5)
[When N-dimethyl-2-amino-7-acetoxytropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 5 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it did not harden even after 30 minutes and remained liquid and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 9 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 19 minutes, it was completely cured and a strong coating film was obtained.
N-dimethyl-2-amino-7-acetoxytropone in cyclohexane solution (0.04 mM) was irradiated with 365 nm ultraviolet light at an intensity of 35 mW / cm ² and its half-life was measured, resulting in 30.1 seconds. Met.

(Example 6)
[When methylamino-formyl-isopropyltropone is used as a photobase generator]
A liquid film having a thickness of 100 μm was formed on the glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm) with the photocurable resin composition 6. Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it was not cured even after 60 minutes and remained in a liquid state and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 20 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 9 minutes, it was completely cured and a strong coating film was obtained.

(Comparative Example 1)
[When N-methyl-2-aminotropone is used as a photobase generator]
A liquid film with a thickness of 100 μm of the photocurable resin composition 7 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it did not harden even after 30 minutes and remained liquid and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 9 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 10 minutes, it was completely cured and a strong coating film was obtained.
The N-methyl-2-aminotropone cyclohexane solution (0.04 mM) was irradiated with 365 nm ultraviolet light at an intensity of 35 mW / cm ² , and its half-life was measured to be 3.32 seconds.

(Comparative Example 2)
[When methylamino-isopropyltropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 8 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). Although this coating film was heated at 120 ° C. without being irradiated with ultraviolet rays, it did not harden even after 30 minutes and remained liquid and a strong coating film could not be obtained.
On the other hand, when a liquid film prepared in the same manner as described above was irradiated with 6 J / cm ² of ultraviolet light (365 nm) in a nitrogen atmosphere, the curing reaction proceeded to form a semi-solid coating film. When this coating film was heated at 120 ° C. for 10 minutes, it was completely cured and a strong coating film was obtained.
It was 3.46 second as a result of irradiating 365 nm ultraviolet-ray with the intensity | strength of 35 mW / cm < ² > with respect to the cyclohexane solution (0.04 mM) of methylamino-isopropyl tropone, and measuring the half life.

(Comparative Example 3)
[When N-methyl-2-amino-3,7-dimethyltropone is used as a photobase generator]
A liquid film having a thickness of 100 μm of the photocurable resin composition 9 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). When this liquid film was heated at 120 ° C. for 1.5 minutes without being irradiated with ultraviolet rays, it was completely cured and a strong coating film was obtained.
4. As a result of measuring the half life of N-methyl-2-amino-3,7-dimethyltropone in cyclohexane solution (0.04 mM) by irradiating 365 nm ultraviolet rays at an intensity of 35 mW / cm ² . It was 76 seconds.

(Comparative Example 4)
[When N-methyl-2-amino-7-methoxytropone is used as a photobase generator]
A 100 μm-thick liquid film of the photocurable resin composition 10 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). When this liquid film was heated at 120 ° C. for 1.5 minutes without being irradiated with ultraviolet rays, it was completely cured and a strong coating film was obtained.
N-methyl-2-amino-7-methoxytropone in cyclohexane solution (0.04 mM) was irradiated with 365 nm ultraviolet light at an intensity of 35 mW / cm ² , and its half-life was measured to be 9.49 seconds. Met.

(Comparative Example 5)
[In the case of N, N′-dimethyl-2-aminotropone]
A liquid film having a thickness of 100 μm of the photocurable resin composition 11 was formed on a glass plate (Pyrex (registered trademark) 60 mm × 60 mm × 2 mm). When this liquid film was heated at 120 ° C. for 1.5 minutes without being irradiated with ultraviolet rays, it was completely cured and a strong coating film was obtained.
It was 31.2 seconds as a result of irradiating 365 nm ultraviolet rays with an intensity of 35 mW / cm ² to a cyclohexane solution (0.04 mM) of N, N′-dimethyl-2-aminotropone and measuring a half-life thereof. .

Tables 2 and 3 show the measurement results of the basic latent in each compound.

First, Examples 1 to 4 and 6 and Comparative Examples 1 to 4 using a 2-aminotropone derivative of a secondary amine were compared.
Examples 1-4 and 6 in which the substituent constant is larger than 0 are the results of short half-life as compared with Comparative Examples 1 to 4 in which the substituent constant is 0 or less, and the generation of base is quick and the curing performance is also high. It was good.
Moreover, although the comparative examples 1 and 2 were made basic latent, since the half life was a little longer compared with Examples 1-4 and 6, it took time for the hardening by the heating after ultraviolet irradiation.
On the other hand, Comparative Examples 3 and 4 did not have a function as a latent curing agent because they had a long half-life and were not made basic latent.

Next, Example 5 and Comparative Example 5 using a 2-aminotropone derivative of a tertiary amine were compared.
Example 5 in which the substituent constant was larger than 0 resulted in a shorter half-life than Comparative Example 5 in which the substituent constant was 0. Further, Example 5 was made basic latent, but Comparative Example 5 was not made basic latent.

  From the above, it was shown that a base is generated at an early stage after light irradiation if it is a photobase generator using 2-aminotropone having at least a substituent constant larger than 0. As a result, it was shown that photocuring can be efficiently and satisfactorily performed.

  INDUSTRIAL APPLICATION This invention can be utilized for the photobase generator suitable for photocuring of anion curable resins, such as an epoxy resin and a polyimide resin, and the photocurable resin composition containing it. In more detail, the present invention expresses or increases basicity while sufficiently suppressing the generation of unnecessary by-products such as gas and water, and insulation reliability, heat resistance, fine workability, etc. are strictly required. The present invention can be used for a photobase generator particularly useful for curing a resin for electronic materials and a photocurable resin composition containing the photobase generator.

Claims (12)

The photobase generator which contains the 2-aminotropone derivative represented by Formula (1) or (2), and whose sum total of the substituent constant of the containing substituent is a value exceeding 0.

(Wherein, _{R 1} and _{R 2} each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl _{group, R 3, R 4, R} 5, R 6 and _{R 7} Each independently represents a hydrogen atom, carboxyl group, alkoxycarbonyl group, cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group, hydroxy group, Represents a mercapto group, an alkylsulfanyl group, an alkoxy group, a halogen atom or an amino group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are saturated when at least two of them are bonded to each other. A hydrogen atom, which may form a ring or an unsaturated ring, each independently a group consisting of a derivative represented by the formula (1) or (2), (A monovalent group from which an atom is eliminated may be substituted. Z represents an oxygen atom or a sulfur atom.)

(In the formula (2), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are Each independently a hydrogen atom, carboxyl group, alkoxycarbonyl group, cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, mercapto group, alkylsulfanyl group, aryl R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent a group, a hydroxy group, an alkoxy group, a halogen atom or an amino group, and at least two of them are bonded to each other. One hydrogen atom, which may form a saturated ring or an unsaturated ring, each independently consisting of a derivative represented by the formula (1) or (2) May have a monovalent group from which is eliminated as a substituent.   The photobase generator according to claim 1, wherein the 2-aminotropone derivative is a secondary amine. The photobase generator according to claim 1 or 2, wherein R _{1 of the} 2-aminotropone derivative represents a methyl group and R ₂ represents a hydrogen atom, or R ₁ represents a hydrogen atom and R ₂ represents a methyl group.   The 2-aminotropone derivatives include N-methyl-2-aminotropone, N-methyl-2-amino-3,5,7-triformyltropone, N-methyl-2-amino-3,7-diformyltropone. N-methyl-2-amino-3,7-diformyltropone, N-methyl-2-amino-methyl acetate tropone, N-methyl-2-amino-4-isopropyl-7-formyltropone and N The photobase generator according to any one of claims 1 to 3, which is at least one compound selected from the group consisting of -methyl-7-amino-3-isopropyl-6-formyltropone.   The photobase generator according to claim 1, wherein the 2-aminotropone derivative is a tertiary amine. The photobase generator according to claim 1 or 5, wherein R ₁ and R ₂ of the 2-aminotropone derivative each represent a methyl group.   The said 2-aminotropone derivative is a compound of at least any one of N, N'-dimethyl-2-aminotropone or N, N'-dimethyl-2-amino-7-acetoxytropone. The photobase generator as described in any one of these. The half-life measured by irradiating a 0.04 mM cyclohexane solution of the 2-aminotropone derivative with ultraviolet light (365 nm) at an intensity of 35 mW / cm ² under a nitrogen atmosphere is less than 3.3 seconds. The photobase generator as described in any one of -7.   A photocurable resin composition comprising at least the photobase generator according to any one of claims 1 to 8 and an anion curable resin.   The photocurable resin composition of Claim 9 which contains 0.001-100 mass parts of said photobase generators with respect to 100 mass parts of anion curable resin.   The photocurable resin composition according to claim 9 or 10, wherein the anion curable resin is a bisphenol A type epoxy resin.   The photocurable resin composition according to any one of claims 9 to 11, further comprising a polythiol.