JP2017155204A - Photocuring composition, compound and base conversion proliferation agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocuring composition having sufficient curability using a photobase generator.SOLUTION: The photocuring composition including an epoxy compound having two or more epoxy groups in one molecule, a photobase generator that generates a base by exposure, and a base conversion proliferation agent that newly generates a base by the action of a base generated from the photobase generator by exposure and the epoxy compound, and newly generates a base also by the action of the newly generated base and the epoxy compound.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable composition, a compound, and a base conversion proliferating agent.

Photo-curing materials that are cured (polymerized) by light irradiation are widely used because they allow precise control of the curing reaction with a relatively simple operation. For example, in the fields of electronic materials and printing materials. It occupies an important position.
Examples of the photocurable material include a radical polymerization photocurable composition containing a photoinitiator that generates radical species upon exposure and a radical polymerizable monomer or oligomer, and an acid upon exposure. An acid-catalyzed photocurable composition containing a photoacid generator and a monomer or oligomer that is cured by the action of an acid has been actively studied.

  On the other hand, base photocatalytic materials containing a photobase generator that generates a base upon exposure and a monomer or oligomer that cures by the action of a base are also known as photocurable materials. As a monomer or oligomer that cures by the action of a base, an epoxy compound having an epoxy group is generally used. As the photobase generator, a nonionic photobase generator that generates a primary amine or a secondary amine by exposure, and a nonionic photobase generator that generates a guanidine type strong base by exposure are known. (See Patent Documents 1 to 3).

J. et al. F. Cameron, J .; M.M. J. et al. Frechet, J. et al. Am. Chem. Soc. 1991, 113, 4303. M.M. Shirai, M .; Tsunooka, Prog. Polym. Sci. 1996, 21, 1. K. Arimitsu, R .; Endo, Chem. Mater. 2013, 25, 4461-4463.

  However, the base catalyst-based photocurable compositions disclosed in Patent Documents 1 to 3 still have room for improvement in curability. In the first place, it is difficult to develop a photobase generator, and it has been a fact that a photocatalytic composition based on a base catalyst has not been sufficiently studied so far. From such a viewpoint, development of a novel base catalyst-based photocurable composition has been desired.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the photocurable composition which has sufficient sclerosis | hardenability using a photobase generator.

In order to solve the above problems, the present invention comprises an epoxy compound having two or more epoxy groups in one molecule, a photobase generator that generates a base by exposure, and a base generated from the photobase generator by exposure, A photocatalyst containing a base conversion growth agent that newly generates a base by the action of the epoxy compound and also generates a new base by the action of the newly generated base and the epoxy compound. A curable composition is provided.
In the photocurable composition of the present invention, the base conversion proliferating agent is preferably a compound represented by the following general formula (1).

（式中、Ｇは有機基であり（ただし、ホルミルアリール基を除く）；Ｘは下記一般式（１）−１１、（１）−１２、（１）−１３又は（１）−１４で表される基である。）

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に水素原子又は炭化水素基であり、Ｒ^１１、Ｒ^１２及びＲ^１３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^３１、Ｒ^３２及びＲ^３３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく；符号＊を付した結合は、Ｘの結合先である炭素原子に対して形成されている。）

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.)

  The present invention also provides a compound represented by the following general formula (1) (excluding 1,1'-carbonyldiimidazole).

（式中、Ｇは有機基であり（ただし、ホルミルアリール基を除く）；Ｘは下記一般式（１）−１１、（１）−１２、（１）−１３又は（１）−１４で表される基である。）

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に水素原子又は炭化水素基であり、Ｒ^１１、Ｒ^１２及びＲ^１３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^３１、Ｒ^３２及びＲ^３３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく；符号＊を付した結合は、Ｘの結合先である炭素原子に対して形成されている。）

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.)

  The compound of the present invention is preferably one represented by the following general formula (1) -1A, (1) -2E, (1) -3A or (1) -4A.

（式中、Ｇは前記と同じであり；Ｒ^１１’、Ｒ^１２’、Ｒ^１３’、Ｒ^３１’、Ｒ^３２’、Ｒ^３３’、Ｒ^４１’、Ｒ^４２’、Ｒ^４３’及びＲ^４４’は、それぞれ独立に水素原子又は炭化水素基であり；Ｒ^０２１及びＲ^０２３は、それぞれ独立に含窒素環である。）

(Wherein G is the same as above; R ¹¹ ′, R ¹² ′, R ¹³ ′, R ³¹ ′, R ³² ′, R ³³ ′, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴⁾ 'Is independently a hydrogen atom or a hydrocarbon group; R ⁰²¹ and R ⁰²³ are each independently a nitrogen-containing ring.)

  The compound of the present invention has the following general formula (1) -1A-1, (1) -1A-2, (1) -1A-3, (1) -2E-1, (1) -3A-1 or ( 1) One or more hydrogen atoms bonded to the carbon atom constituting the nitrogen-containing ring skeleton of the compound represented by -4A-1 or the compound represented by the following general formula (1) -2E-1 A compound substituted with an alkyl group having 1 to 5 carbon atoms is preferable.

（式中、ｎ_１は０〜５の整数であり；Ｚ^１はアルコキシ基、アリールオキシ基又はニトロ基であり、ｎ_１が２〜５の整数である場合、複数個のＺ^１は互いに同一でも異なっていてもよく；Ｒ^１１’、Ｒ^１２’、Ｒ^３１’、Ｒ^３２’、Ｒ^３３’、Ｒ^４１’、Ｒ^４２’、Ｒ^４３’及びＲ^４４’は、それぞれ独立に水素原子又は炭化水素基である。）

(In the formula, n ₁ is an integer of 0 to 5; Z ¹ is an alkoxy group, an aryloxy group or a nitro group, and when n ₁ is an integer of 2 to 5, a plurality of Z ¹ are the same as each other) R ¹¹ ′, R ¹² ′, R ³¹ ′, R ³² ′, R ³³ ′, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ may each independently represent a hydrogen atom or It is a hydrocarbon group.)

Further, the present invention comprises a compound represented by the following general formula (1),
Base conversion that generates a new base by the action of a base and an epoxy compound having an epoxy group, and also generates a new base by the action of the newly generated base and the epoxy compound. Proliferating agent is provided.

（式中、Ｇは有機基であり（ただし、ホルミルアリール基を除く）；Ｘは下記一般式（１）−１１、（１）−１２、（１）−１３又は（１）−１４で表される基である。）

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に水素原子又は炭化水素基であり、Ｒ^１１、Ｒ^１２及びＲ^１３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^３１、Ｒ^３２及びＲ^３３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく；符号＊を付した結合は、Ｘの結合先である炭素原子に対して形成されている。）

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.)

  According to the present invention, a photocurable composition having sufficient curability using a photobase generator is provided.

It is an analysis result of ¹ H-NMR in Test Example 1. It is an analysis result of ¹ H-NMR in Test Example 2.

<Compound (1)>
The compound of the present invention (sometimes referred to as “compound (1)” in the present specification) is represented by the following general formula (1). However, 1,1′-carbonyldiimidazole, which is a known compound, is excluded.

（式中、Ｇは有機基であり（ただし、ホルミルアリール基を除く）；Ｘは下記一般式（１）−１１、（１）−１２、（１）−１３又は（１）−１４で表される基である。）

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に水素原子又は炭化水素基であり、Ｒ^１１、Ｒ^１２及びＲ^１３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^３１、Ｒ^３２及びＲ^３３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく；符号＊を付した結合は、Ｘの結合先である炭素原子に対して形成されている。）

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.)

The compound (1) is a compound represented by the general formula (1) and having a carboxylic acid amide bond formed by bonding a nitrogen atom in X and a carbon atom of a carbonyl group.
Further, in the compound (1), the bond between the carbonyl group and X described in the general formula (1) was cleaved under specific conditions, and the X was bonded to the carbon atom of the carbonyl group. The nitrogen atom in the inside has a common property that a basic compound having a structure bonded to a hydrogen atom (in this specification, simply abbreviated as “base”) is generated. This characteristic will be described in detail later.

[Compound (1)]
The compound (1) is represented by the general formula (1).
In General Formula (1), G is an organic group, and is a monovalent group containing a carbon atom as a constituent atom, and is not particularly limited as long as it is other than a formylaryl group. For example, an aliphatic group and an aromatic group Any of the groups may be used. In this specification, the “formylaryl group” means that a hydrogen atom bonded to a carbon atom constituting the ring skeleton of an aryl group is substituted with a formyl group (—C (═O) —H). Means the group

  As said organic group, the hydrocarbon group which may have a substituent is mentioned, for example. Here, “the hydrocarbon group has a substituent” means that one or more hydrogen atoms constituting the hydrocarbon group are substituted with a group (substituent) other than a hydrogen atom, or constitute a hydrocarbon group One or more carbon atoms, or together with one or more hydrogen atoms to which the carbon atom is bonded, different from this (a carbon atom or a carbon atom to which one or more hydrogen atoms are bonded) It means being substituted with a group (substituent). And both a hydrogen atom and a carbon atom may be substituted by the substituent.

  The hydrocarbon group in G may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group (aryl group), and is an aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group. It may be a polycyclic hydrocarbon group formed by condensation of a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group.

  The aliphatic hydrocarbon group for G may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.

  The alkyl group in G may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. The alkyl group preferably has 1 to 20 carbon atoms.

  The linear or branched alkyl group preferably has 1 to 20 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methyl Pentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl Group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl , Isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.

  The cyclic alkyl group preferably has 3 to 20 carbon atoms. Examples of the alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. , A cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, a tricyclodecyl group, and the like. Furthermore, one or more hydrogen atoms of these cyclic alkyl groups are linear, branched Examples thereof include those substituted with a chain or cyclic alkyl group. Here, examples of the linear, branched and cyclic alkyl groups for substituting a hydrogen atom include those described above as examples of the alkyl group in G.

The unsaturated aliphatic hydrocarbon group for G may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. The unsaturated aliphatic hydrocarbon group preferably has 2 to 20 carbon atoms.
The unsaturated aliphatic hydrocarbon group for G is a double bond (C═C) in which one or more single bonds (C—C) between carbon atoms in the alkyl group for G are unsaturated bonds. ) Or a group substituted with a triple bond (C≡C).
In the unsaturated aliphatic hydrocarbon group, the number of unsaturated bonds may be one, two or more, and when two or more, these unsaturated bonds may be only double bonds or triple bonds. Only a bond may be sufficient, and a double bond and a triple bond may be mixed.
In the unsaturated aliphatic hydrocarbon group, the position of the unsaturated bond is not particularly limited.

Preferred examples of the unsaturated aliphatic hydrocarbon group for G include linear or branched alkenyl groups and alkynyl groups corresponding to one unsaturated bond, and cyclic groups. And cycloalkenyl groups and cycloalkynyl groups which are
Examples of the alkenyl group include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a cyclohexenyl group, and the like.

  The aryl group in G may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms. Examples of such an aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group), and the like. Examples include those in which one or more hydrogen atoms of these aryl groups are further substituted with these aryl groups or the alkyl group in G. The aryl group having these substituents preferably has 6 to 20 carbon atoms including the substituents.

  Among the hydrocarbon groups in G, the aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group (aryl group) is, for example, one having 1 hydrogen atom substitution. If present, arylalkyl groups (aralkyl groups) such as phenylmethyl group (benzyl group) and 2-phenylethyl group (phenethyl group) can be mentioned.

  Examples of the substituent in which one or more hydrogen atoms are substituted in the hydrocarbon group include an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylcarbonyl group, and an arylcarbonyl group. , Alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, arylthio group, cyano group (-CN), halogen atom, nitro group, haloalkyl group (halogenated alkyl group), hydroxyl group (-OH), a mercapto group (-SH), etc. are mentioned.

In the hydrocarbon group, the number of substituents replacing hydrogen atoms may be one, or two or more, and all hydrogen atoms may be substituted with the substituents.
In the hydrocarbon group, when there are two or more substituents replacing a hydrogen atom, these substituents may all be the same, may be all different, or only partially the same. Also good.

Examples of the alkoxy group as a substituent include monovalent groups formed by bonding the alkyl group in G to an oxygen atom, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a cyclopropoxy group. Can be mentioned.
Examples of the aryloxy group that is a substituent include a monovalent formed by bonding the aryl group in G to an oxygen atom, such as a phenyloxy group (phenoxy group), 1-naphthyloxy group, and 2-naphthyloxy group. Groups.

Examples of the dialkylamino group as a substituent include a monovalent group in which two hydrogen atoms of an amino group (—NH ₂ ) such as a dimethylamino group and a methylethylamino group are substituted with the alkyl group in G. The group of is mentioned. In the dialkylamino group, two alkyl groups bonded to the nitrogen atom may be the same as or different from each other.
Examples of the diarylamino group as a substituent include a monovalent group formed by replacing two hydrogen atoms of an amino group with the aryl group in G, such as a diphenylamino group and a phenyl-1-naphthylamino group. Is mentioned. In the diarylamino group, two aryl groups bonded to the nitrogen atom may be the same as or different from each other.
Examples of the alkylarylamino group that is a substituent include one hydrogen atom of two hydrogen atoms of an amino group such as a methylphenylamino group, and the like. A monovalent group in which an atom is substituted with the aryl group in G is mentioned.

Examples of the alkylcarbonyl group as a substituent include a monovalent group formed by bonding the alkyl group in G to a carbonyl group (—C (═O) —) such as a methylcarbonyl group (acetyl group). It is done.
Examples of the arylcarbonyl group as a substituent include monovalent groups formed by bonding the aryl group in G to a carbonyl group, such as a phenylcarbonyl group (benzoyl group).

Examples of the alkyloxycarbonyl group as a substituent include monovalent groups formed by bonding the alkoxy group to a carbonyl group, such as a methyloxycarbonyl group (methoxycarbonyl group).
Examples of the aryloxycarbonyl group as a substituent include monovalent groups formed by bonding the aryloxy group to a carbonyl group, such as a phenyloxycarbonyl group (phenoxycarbonyl group).

Examples of the alkylcarbonyloxy group as a substituent include a monovalent group formed by bonding the alkyl group to a carbon atom of a carbonyloxy group (—C (═O) —O—) such as a methylcarbonyloxy group. Is mentioned.
Examples of the arylcarbonyloxy group as a substituent include monovalent groups formed by bonding the aryl group to a carbon atom of the carbonyloxy group, such as a phenylcarbonyloxy group.

Examples of the alkylthio group as a substituent include a monovalent group in which the alkyl group in G is bonded to a sulfur atom, such as a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, and a cyclopropylthio group. Is mentioned.
Examples of the arylthio group as a substituent include monovalent groups formed by bonding the aryl group in G to a sulfur atom, such as a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

  As said halogen atom which is a substituent, a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I) are mentioned, for example.

Examples of the haloalkyl group as a substituent include a group in which one or more hydrogen atoms of the alkyl group in G are substituted with a halogen atom.
Examples of the halogen atom in the haloalkyl group include those exemplified above as the halogen atom as the substituent.
The number of halogen atoms in the haloalkyl group is not particularly limited, and may be 1 or 2 or more. When the number of halogen atoms in the haloalkyl group is 2 or more, the plurality of halogen atoms may be all the same, all may be different, or only a part may be the same. The haloalkyl group may be a perhaloalkyl group in which all hydrogen atoms in the alkyl group are substituted with halogen atoms.
Examples of the haloalkyl group include, but are not limited to, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group.

  In the hydrocarbon group, the number of substituents replacing hydrogen atoms is preferably 1 to 4, more preferably 1 to 3, although it depends on the number of substitutable hydrogen atoms. It is particularly preferable that the number is 1 or 2.

  Examples of the substituent in which one or more carbon atoms or one or more hydrogen atoms bonded to the carbon atom are substituted in the hydrocarbon group include a nitrogen atom, an oxygen atom, and a sulfur atom. And the like.

In the hydrocarbon group, the substituent for substituting a carbon atom or a carbon atom to which a hydrogen atom is bonded may be only one, may be two or more, and all the carbon atoms are singly or the carbon atom. A hydrogen atom bonded to may be substituted with a substituent.
In the hydrocarbon group, when there are two or more substituents replacing a carbon atom or a carbon atom to which a hydrogen atom is bonded, these substituents may all be the same or different. Alternatively, only a part may be the same.

Among the hydrocarbon groups substituted with a heteroatom, an aromatic hydrocarbon group, that is, an aromatic heterocyclic group (heteroaryl group) is composed of various aromatic heterocyclic compounds and its ring skeleton. And a group formed by removing one hydrogen atom bonded to a carbon atom or a hetero atom.
Preferred examples of the aromatic heterocyclic compound include sulfur-containing aromatic heterocyclic compounds (compounds having one or more sulfur atoms as atoms constituting the aromatic heterocyclic skeleton), nitrogen-containing aromatic heterocyclic compounds (aromatic Compounds having one or more nitrogen atoms as atoms constituting the aromatic heterocyclic skeleton), oxygen-containing aromatic heterocyclic compounds (compounds having one or more oxygen atoms as the atoms constituting the aromatic heterocyclic skeleton), sulfur The compound which has two different hetero atoms selected from an atom, a nitrogen atom, and an oxygen atom as an atom which comprises an aromatic heterocyclic skeleton is mentioned.

  Examples of the sulfur-containing aromatic heterocyclic compound include thiophene and benzothiophene.

  Examples of the nitrogen-containing aromatic heterocyclic compound include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, benzimidazole, purine, indazole, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline. Etc.

  Examples of the oxygen-containing aromatic heterocyclic compound include furan, benzofuran (1-benzofuran), isobenzofuran (2-benzofuran), and the like.

  Examples of the compound having two different heteroatoms as atoms constituting the aromatic heterocyclic skeleton include oxazole, isoxazole, thiazole, benzoxazole, benzoisoxazole, and benzothiazole.

  In the hydrocarbon group, the number of the substituents replacing the carbon atom or the carbon atom to which the hydrogen atom is bonded is preferably 1 to 3, although it depends on the substitutable carbon atom. Two is more preferable.

G is preferably an optionally substituted alkyl group, alkenyl group, aryl group, heteroaryl group, or arylalkyl group. The substituent here is the same as the above-described substituent described as having a hydrocarbon group.
Among them, G is an alkyl which may have one or two or more in total selected from the group consisting of an alkoxy group, an aryloxy group and a nitro group as a substituent. More preferably a group, an alkenyl group, an aryl group, a heteroaryl group or an arylalkyl group, and one or more selected from the group consisting of an alkoxy group, an aryloxy group and a nitro group as a substituent. Further, an alkyl group, an aryl group, a heteroaryl group or an arylalkyl group which may have one or two or more in total is more preferable.

  Among them, G is an alkyl which may have one or two or more in total selected from the group consisting of an alkoxy group, an aryloxy group and a nitro group as a substituent. It is more preferably a group or an aryl group, and it has one or two or more in total selected from the group consisting of an alkoxy group, an aryloxy group and a nitro group as a substituent. It is more preferable that it is an aryl group which may be present, and examples of such G include a group represented by the following general formula (1) -21.

（式中、ｎ_１は０〜５の整数であり；Ｚ^１はアルコキシ基、アリールオキシ基又はニトロ基であり、ｎ_１が２〜５の整数である場合、複数個のＺ^１は互いに同一でも異なっていてもよく；符号＊＊を付した結合は、Ｇの結合先である炭素原子に対して形成されている。）

(In the formula, n ₁ is an integer of 0 to 5; Z ¹ is an alkoxy group, an aryloxy group or a nitro group, and when n ₁ is an integer of 2 to 5, a plurality of Z ¹ are the same as each other) But may be different; the bond marked ** is formed to the carbon atom to which G is attached.)

In General Formula (1) -21, n ₁ is an integer of 0 to 5, and represents the number of bonds of Z ^{1 to} the benzene ring skeleton.
n ₁ is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably an integer of 0 to 2, and particularly preferably 0 or 1.

In General Formula (1) -21, Z ¹ is an alkoxy group, an aryloxy group, or a nitro group, and among these, the alkoxy group and the aryloxy group are the alkoxy group and aryloxy group that G described above has as a substituent. Is the same.
If n ₁ is an integer from 2 to 5, a plurality of Z ¹ may be the same or different from each other. That is, in this case, all Z ¹ may be the same, all may be different, or only a part may be the same.
When n ₁ is an integer of ₁ to 4, the bonding position of Z ^{1 to} the benzene ring skeleton is not particularly limited.

  In general formula (1) -21, the bond denoted by ** is attached to the carbon atom to which G is bonded, that is, the carbon atom in the carbonyl group to which X is bonded in general formula (1). It is formed against.

  In General Formula (1), X is a group represented by General Formula (1) -11, (1) -12, (1) -13, or (1) -14. The bond with the symbol * is formed with respect to the carbon atom to which X is bonded, that is, the carbon atom in the carbonyl group to which G is bonded in the general formula (1).

In general formula (1) -11, (1) -12, (1) -13 or (1) -14, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or a hydrocarbon group.
That is, in the general formula (1) -11, R ¹¹ , R ¹² and R ¹³ (hereinafter sometimes abbreviated as “R ^{11 to} R ¹³ ”) may all be the same or different. It may be the same or only part of it may be the same.
Similarly, in the general formula (1) -12, all of R ²¹ , R ²² , R ²³ and R ²⁴ (hereinafter sometimes abbreviated as “R ^{21 to} R ²⁴ ”) may be the same. , All may be different or only some may be the same.
Similarly, in the general formula (1) -13, R ³¹ , R ³² and R ³³ (hereinafter sometimes abbreviated as “R ^{31 to} R ³³ ”) may all be the same or different. Or only part of them may be the same.
Similarly, in the general formula (1) -14, R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ (hereinafter may be abbreviated as “R ^{41 to} R ⁴⁴ ”) may all be the same. , All may be different or only some may be the same.

The hydrocarbon group in R ^{11 to} R ¹³ , R ^{21 to} R ²⁴ , R ^{31 to} R ³³ , and R ^{41 to} R ⁴⁴ is the same as the hydrocarbon group in G described above except that it has no substituent. Is.
That is, examples of the hydrocarbon group in R ^{11 to} R ¹³ , R ^{21 to} R ²⁴ , R ^{31 to} R ³³ , and R ^{41 to} R ⁴⁴ include an alkyl group (saturated aliphatic hydrocarbon group); An unsaturated aliphatic hydrocarbon group in which one or more single bonds between carbon atoms are substituted with double bonds or triple bonds; an aryl group; one or more hydrogen atoms are replaced with an aryl group An aliphatic hydrocarbon group; a polycyclic hydrocarbon group formed by condensation of a cyclic aliphatic hydrocarbon group and an aryl group.

In General Formula (1) -11, when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups are bonded to each other, and these hydrocarbon groups are bonded to each other. A ring may be formed together with carbon atoms (carbon atoms constituting the imidazole skeleton). Here, “two or more hydrocarbon groups are bonded to each other” means that only two or all (three) of R ^{11 to} R ¹³ are hydrocarbon groups, and any two of the carbon groups There are cases where only hydrogen groups are bonded to each other and cases where all (three types) of R ^{11 to} R ¹³ are hydrocarbon groups, and all these hydrocarbon groups are bonded to each other. In any case, these hydrocarbon groups are bonded to each other.

  When two or more hydrocarbon groups are bonded to each other, the position (bonding position) of the bonding carbon atom is not particularly limited. For example, when the hydrocarbon group to be bonded is linear or branched, the bonding position may be the terminal carbon atom of the hydrocarbon group or constitutes the imidazole skeleton of the hydrocarbon group. The carbon atom may be a so-called root carbon atom directly bonded to the carbon atom, or may be a carbon atom at an intermediate position between the terminal and the root. On the other hand, when the hydrocarbon group to be bonded has a cyclic structure or has both a chain structure and a cyclic structure, the bonding position may be a root carbon atom or other carbon atoms. Also good.

When two hydrocarbon groups of R ^{11 to} R ¹³ are bonded to each other, the ring formed thereby may be either monocyclic or polycyclic. The group represented by the general formula (1) -11 has a structure in which an imidazole skeleton and a ring formed by mutual bonding of these hydrocarbon groups are condensed.

In General Formula (1) -12, when two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups are bonded to each other, and these hydrocarbon groups are A ring may be formed together with the bonded nitrogen atom and the carbon atom bonded to the nitrogen atom (the same carbon atom in which three nitrogen atoms are bonded together). Here, “two or more types of hydrocarbon groups are bonded to each other” means the same as the case where any of the hydrocarbon groups of R ^{11 to} R ¹³ are bonded to each other as described above. For example, in order to bind in this way, only two of R ^{21 to} R ²⁴ , only three or all (four) are hydrocarbon groups, and any two or three hydrocarbon groups Only when they are bonded to each other, and all (4 types) of R ^{21 to} R ²⁴ are hydrocarbon groups, and all these hydrocarbon groups may be bonded to each other. The method is the same as in the case of R ^{11 to} R ¹³ .

In General Formula (1) -13, when two or more of R ³¹ , R ³² and R ³³ are hydrocarbon groups, these hydrocarbon groups are bonded to each other, and these hydrocarbon groups are bonded to each other. A ring may be formed together with the nitrogen atom or carbon atom and the carbon atom bonded to the nitrogen atom or the nitrogen atom bonded to the carbon atom. Here, “two or more types of hydrocarbon groups are bonded to each other” means the same as the case where any of the hydrocarbon groups of R ^{11 to} R ¹³ are bonded to each other as described above. For example, in such a case, only two or all (three) of R ^{31 to} R ³³ are hydrocarbon groups, and only two of these hydrocarbon groups are bonded to each other. And all of R ^{31 to} R ³³ (3 types) are hydrocarbon groups, and all these hydrocarbon groups may be bonded to each other, and the bonding method between the hydrocarbon groups is also R ^{11 to} R ^This is the same as the case of ¹³ .

In General Formula (1) -14, when two or more of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are hydrocarbon groups, these hydrocarbon groups are bonded to each other, and these hydrocarbon groups are A ring may be formed together with the bonded nitrogen atom and the carbon atom bonded to the nitrogen atom (the same carbon atom in which three nitrogen atoms are bonded together). Here, “two or more types of hydrocarbon groups are bonded to each other” means the same as the case where any of the hydrocarbon groups of R ^{11 to} R ¹³ are bonded to each other as described above. For example, only two of R ^{41 to} R ⁴⁴ , only three or all (four) are hydrocarbon groups, and any two or three hydrocarbon groups can be bonded in this way. Only when they are bonded to each other, and all (4 types) of R ^{41 to} R ⁴⁴ are hydrocarbon groups, and all these hydrocarbon groups may be bonded to each other. The method is the same as in the case of R ^{11 to} R ¹³ .

  The compound (1) is represented by the following general formula (1) -1 (hereinafter sometimes abbreviated as “compound (1) -1”), and the following general formula (1) -2. Compound (hereinafter sometimes abbreviated as “compound (1) -2”), compound represented by the following general formula (1) -3 (hereinafter abbreviated as “compound (1) -3”) ) And a compound represented by the following general formula (1) -4 (hereinafter sometimes abbreviated as “compound (1) -4”).

  As described above, the compound (1) of the present invention does not include 1,1′-carbonyldiimidazole. Therefore, in the compound (1) of the present invention, G and X are not both imidazol-1-yl groups.

（式中、Ｇ、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、前記と同じである。）

(In the formula, G, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are Is the same.)

  Preferred examples of the compound (1) -1 include a compound represented by the following general formula (1) -1A (hereinafter sometimes abbreviated as “compound (1) -1A”), and the following general formula: (1) -1B (hereinafter, may be abbreviated as “compound (1) -1B”).

（式中、Ｇは前記と同じであり；Ｒ^１１’、Ｒ^１２’及びＲ^１３’は、それぞれ独立に水素原子又は炭化水素基であり；Ｒ^０１１は炭化水素環である。）

(In the formula, G is the same as above; R ¹¹ ′, R ¹² ′ and R ¹³ ′ are each independently a hydrogen atom or a hydrocarbon group; R ⁰¹¹ is a hydrocarbon ring.)

In the general formulas (1) -1A to (1) -1B, R ¹¹ ′, R ¹² ′ and R ¹³ ′ are each independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon groups in R ¹¹ ′, R ¹² ′ and R ¹³ ′ are the same as the hydrocarbon groups in R ^{11 to} R ¹³ described above except that they do not bind to each other to form a ring. . That is, the compound (1) -1A has a structure in which the imidazole skeleton described in the general formula (1) -1A is condensed, regardless of which group R ¹¹ ′, R ¹² ′ and R ¹³ ′ are any groups. Does not have.
In general formulas (1) -1A to (1) -1B, R ¹¹ ′, R ¹² ′ and R ¹³ ′ are preferably a hydrogen atom, an alkyl group or an aryl group.

In general formula (1) -1B, R ⁰¹¹ is a hydrocarbon ring. That is, in the general formula (1) -1B, R ⁰¹¹ represents a hydrocarbon ring (cyclic) that is condensed with the imidazole skeleton by sharing two adjacent carbon atoms in the imidazole skeleton with the imidazole skeleton. Hydrocarbon group).
Compound (1) -1B is a compound (1) -1 in which R ¹² and R ¹³ which are hydrocarbon groups are bonded to each other to form a ring.
In general formula (1) -1B, R ⁰¹¹ may be monocyclic or polycyclic, and may be a saturated aliphatic hydrocarbon ring such as a cyclohexane ring, or an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring. Is preferred.

Preferred examples of compound (1) -1A include those in which at least one of R ¹¹ ′, R ¹² ′ and R ¹³ ′ is a hydrogen atom.
Preferred examples of compound (1) -1B include those in which R ⁰¹¹ is an aromatic hydrocarbon ring.

  More preferable compound (1) -1 is an alkyl having 1 to 5 carbon atoms in which the following compounds and one or more hydrogen atoms bonded to the carbon atoms constituting the nitrogen-containing ring skeleton of these compounds are bonded. And those substituted with a group. Here, the “nitrogen-containing ring skeleton” constitutes X in the general formula (1).

（式中、ｎ_１、Ｚ^１、Ｒ^１１’及びＲ^１２’は前記と同じである。）

(In the formula, n ₁ , Z ¹ , R ¹¹ ′ and R ¹² ′ are the same as described above.)

  Preferred examples of the compound (1) -2 include a compound represented by the following general formula (1) -2A (hereinafter sometimes abbreviated as “compound (1) -2A”), the following general formula ( 1) a compound represented by -2B (hereinafter sometimes abbreviated as "compound (1) -2B"), a compound represented by the following general formula (1) -2C (hereinafter "compound (1)-" 2C "), a compound represented by the following general formula (1) -2D (hereinafter sometimes abbreviated as" compound (1) -2D "), and the following general formula (1)- 2E (hereinafter sometimes abbreviated as “compound (1) -2E”).

（式中、Ｇは前記と同じであり；Ｒ^２１’、Ｒ^２２’、Ｒ^２３’及びＲ^２４’は、それぞれ独立に水素原子又は炭化水素基であり；Ｒ^０２１、Ｒ^０２２及びＲ^０２３は、それぞれ独立に含窒素環である。）

(In the formula, G is the same as above; R ²¹ ′, R ²² ′, R ²³ ′ and R ²⁴ ′ are each independently a hydrogen atom or a hydrocarbon group; R ⁰²¹ , R ⁰²² and R ⁰²³ are And each independently a nitrogen-containing ring.)

In the general formulas (1) -2A to (1) -2E, R ²¹ ′, R ²² ′, R ²³ ′ and R ²⁴ ′ are each independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon groups in R ^{11 to} R ¹³ described above, except that the hydrocarbon groups in R ²¹ ′, R ²² ′, R ²³ ′, and R ²⁴ ′ are not bonded to each other to form a ring. Is the same.
In general formulas (1) -2A to (1) -2E, R ²¹ ′, R ²² ′, R ²³ ′ and R ²⁴ ′ are preferably a hydrogen atom, an alkyl group or an aryl group, and an alkyl group or an aryl group More preferably, it is a group.

In General Formula (1) -2B, R ⁰²¹ is a nitrogen-containing ring. In the present specification, the “nitrogen-containing ring” means a cyclic structure having a nitrogen atom in addition to a carbon atom and a hydrogen atom. That is, in the general formula (1) -2B, R ⁰²¹ includes a nitrogen atom bonded to the carbon atom of the carbonyl group described in the general formula, a nitrogen atom bonded to R ²³ ′, It is a ring structure (nitrogen-containing cyclic group) in which one carbon atom located between these two nitrogen atoms is a constituent atom of the ring skeleton. R ⁰²¹ may be monocyclic or polycyclic, and is usually an aliphatic nitrogen-containing ring.
Compound (1) -2B is a compound (1) -2 in which R ²¹ and R ²² which are hydrocarbon groups are bonded to each other to form a ring.

In general formula (1) -2C, R ⁰²² is a nitrogen-containing ring. That is, in the general formula (1) -2C, R ⁰²² is one nitrogen atom in which R ²¹ ′ and R ²⁴ ′ are not bonded to each other among the three nitrogen atoms described in the general formula. Is a ring structure (nitrogen-containing cyclic group) having a ring skeleton as a constituent atom. R ⁰²² may be monocyclic or polycyclic, and may be either an aliphatic nitrogen-containing ring or an aromatic nitrogen-containing ring.
Compound (1) -2C is a compound (1) -2 in which R ²² and R ²³ which are hydrocarbon groups are bonded to each other to form a ring.

In general formula (1) -2D, R ⁰²³ is a nitrogen-containing ring. That is, in General Formula (1) -2D, R ⁰²³ includes two nitrogen atoms to which R ²¹ ′ is not bonded, and two of these three nitrogen atoms described in the general formula. A ring structure (nitrogen-containing cyclic group) in which one carbon atom located between the nitrogen atoms is a constituent atom of the ring skeleton. R ⁰²³ may be monocyclic or polycyclic, and may be either an aliphatic nitrogen-containing ring or an aromatic nitrogen-containing ring.
Compound (1) -2D is a compound (1) -2 in which R ²³ and R ²⁴ which are hydrocarbon groups are bonded to each other to form a ring.

In General Formula (1) -2E, R ⁰²¹ and R ⁰²³ are nitrogen-containing rings, R ⁰²¹ is the same as R ⁰²¹ in General Formula (1) -2B, and R ⁰²³ is General Formula (1) -2D. The same as R ^{023 in the} middle.
In compound (1) -2E, among compounds (1) -2, R ²¹ and R ²² which are hydrocarbon groups are bonded to each other to form a ring, and R ²³ and R ²⁴ which are hydrocarbon groups are mutually bonded. To form a ring.

Preferred examples of compound (1) -2A include those in which R ²¹ ′, R ²² ′, R ²³ ′ and R ²⁴ ′ are all alkyl groups or aryl groups.
Preferred examples of compound (1) -2C include those wherein R ⁰²² is an aliphatic nitrogen-containing ring.
Preferred examples of compound (1) -2D include those wherein R ⁰²³ is an aliphatic nitrogen-containing ring.
Preferred examples of compound (1) -2E include those in which R ⁰²³ is an aliphatic nitrogen-containing ring (both R ⁰²¹ and R ⁰²³ are aliphatic nitrogen-containing rings).

  More preferable compound (1) -2 is an alkyl having 1 to 5 carbon atoms in which the following compounds and one or more hydrogen atoms bonded to the carbon atoms constituting the nitrogen-containing ring skeleton of these compounds are bonded. And those substituted with a group. Here, the “nitrogen-containing ring skeleton” constitutes X in the general formula (1).

（式中、ｎ_１、Ｚ^１、Ｒ^２１’、Ｒ^２２’、Ｒ^２３’及びＲ^２４’は前記と同じである。）

(In the formula, n ₁ , Z ¹ , R ²¹ ′, R ²² ′, R ²³ ′ and R ²⁴ ′ are the same as described above.)

  Preferred examples of the compound (1) -3 include a compound represented by the following general formula (1) -3A (hereinafter sometimes abbreviated as “compound (1) -3A”), the following general formula ( 1) a compound represented by -3B (hereinafter sometimes abbreviated as “compound (1) -3B”), a compound represented by the following general formula (1) -3C (hereinafter, “compound (1) — 3C ”), and a compound represented by the following general formula (1) -3D (hereinafter sometimes abbreviated as“ compound (1) -3D ”).

（式中、Ｇは前記と同じであり；Ｒ^３１’、Ｒ^３２’及びＲ^３３’は、それぞれ独立に水素原子又は炭化水素基であり；Ｒ^０３１、Ｒ^０３２及びＲ^０３３は、それぞれ独立に含窒素環である。）

(In the formula, G is the same as above; R ³¹ ′, R ³² ′ and R ³³ ′ are each independently a hydrogen atom or a hydrocarbon group; R ⁰³¹ , R ⁰³² and R ⁰³³ are each independently (It is a nitrogen-containing ring.)

In the general formulas (1) -3A to (1) -3D, R ³¹ ′, R ³² ′ and R ³³ ′ are each independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon groups in R ³¹ ′, R ³² ′, and R ³³ ′ are the same as the hydrocarbon groups in R ^{11 to} R ¹³ described above, except that they do not bind to each other to form a ring. .
In general formulas (1) -3A to (1) -3D, R ³¹ ′, R ³² ′ and R ³³ ′ are preferably a hydrogen atom, an alkyl group or an aryl group.

In general formula (1) -3B, R ⁰³¹ is a nitrogen-containing ring. That is, in General Formula (1) -3B, R ⁰³¹ includes one nitrogen atom to which R ³¹ ′ is not bonded, and two of these two nitrogen atoms described in the general formula. A ring structure (nitrogen-containing cyclic group) in which one carbon atom located between the nitrogen atoms is a constituent atom of the ring skeleton. R ⁰³¹ may be monocyclic or polycyclic, and may be either an aliphatic nitrogen-containing ring or an aromatic nitrogen-containing ring.
Compound (1) -3B is a compound (1) -3 in which R ³² and R ³³ which are hydrocarbon groups are bonded to each other to form a ring.

In general formula (1) -3C, R ⁰³² is a nitrogen-containing ring. That is, in the general formula (1) -3C, R ⁰³² represents two nitrogen atoms described in the general formula and one carbon atom located between the two nitrogen atoms. It is a ring structure (nitrogen-containing cyclic group) as a constituent atom of the skeleton. R ⁰³² may be monocyclic or polycyclic, and may be either an aliphatic nitrogen-containing ring or an aromatic nitrogen-containing ring.
Compound (1) -3C is a compound (1) -3 in which R ³¹ and R ³³ which are hydrocarbon groups are bonded to each other to form a ring.

In general formula (1) -3D, R ⁰³³ is a nitrogen-containing ring. That is, in General Formula (1) -3D, R ⁰³³ includes one nitrogen atom to which R ³³ ′ is not bonded, and two of these two nitrogen atoms described in the general formula. A ring structure (nitrogen-containing cyclic group) in which one carbon atom located between the nitrogen atoms is a constituent atom of the ring skeleton. R ⁰³³ may be monocyclic or polycyclic, and is usually an aliphatic nitrogen-containing ring.
Compound (1) -3D is a compound (1) -3 in which R ³¹ and R ³² which are hydrocarbon groups are bonded to each other to form a ring.

Preferred examples of compound (1) -3A include those in which at least one of R ³¹ ′, R ³² ′ and R ³³ ′ is a hydrogen atom.
Preferred examples of compound (1) -3B include those in which R ⁰³¹ is an aliphatic nitrogen-containing ring.
Preferred examples of compound (1) -3C include those in which R ⁰³² is an aliphatic nitrogen-containing ring.

  More preferable compound (1) -3 is an alkyl having 1 to 5 carbon atoms in which the following compounds and one or more hydrogen atoms bonded to the carbon atoms constituting the nitrogen-containing ring skeleton of these compounds are bonded. And those substituted with a group. Here, the “nitrogen-containing ring skeleton” constitutes X in the general formula (1).

（式中、ｎ_１、Ｚ^１、Ｒ^３１’、Ｒ^３２’及びＲ^３３’は前記と同じである。）

(In the formula, n ₁ , Z ¹ , R ³¹ ′, R ³² ′ and R ³³ ′ are the same as described above.)

  Preferred examples of the compound (1) -4 include a compound represented by the following general formula (1) -4A (hereinafter sometimes abbreviated as “compound (1) -4A”), the following general formula ( 1) a compound represented by -4B (hereinafter sometimes abbreviated as “compound (1) -4B”), a compound represented by the following general formula (1) -4C (hereinafter referred to as “compound (1) — 4C "), a compound represented by the following general formula (1) -4D (hereinafter sometimes abbreviated as" compound (1) -4D "), and the following general formula (1)- 4E (hereinafter sometimes abbreviated as “compound (1) -4E”).

（式中、Ｇは前記と同じであり；Ｒ^４１’、Ｒ^４２’、Ｒ^４３’及びＲ^４４’は、それぞれ独立に水素原子又は炭化水素基であり；Ｒ^０４１、Ｒ^０４２及びＲ^０４３は、それぞれ独立に含窒素環である。）

(Wherein G is the same as above; R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ are each independently a hydrogen atom or a hydrocarbon group; R ⁰⁴¹ , R ⁰⁴² and R ⁰⁴³ are And each independently a nitrogen-containing ring.)

In the general formulas (1) -4A to (1) -4E, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ are each independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon groups in R ^{11 to} R ¹³ described above, except that the hydrocarbon groups in R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ do not bind to each other to form a ring. Is the same.
In the general formulas (1) -4A to (1) -4E, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ are preferably a hydrogen atom, an alkyl group or an aryl group, and an alkyl group or an aryl group More preferably, it is a group.

In general formula (1) -4B, R ⁰⁴¹ is a nitrogen-containing ring. That is, in the general formula (1) -4B, R ⁰⁴¹ represents a nitrogen atom bonded to the carbon atom of the carbonyl group among the three nitrogen atoms described in the general formula, R ⁴³ ′ and A ring structure (nitrogen-containing cyclic group) in which R ⁴⁴ ′ is bonded to a nitrogen atom and a nitrogen atom not corresponding to any of them is a constituent atom of the ring skeleton. R ⁰⁴¹ may be monocyclic or polycyclic, and may be either an aliphatic nitrogen-containing ring or an aromatic nitrogen-containing ring.
Compound (1) -4B is a compound (1) -4 in which R ⁴¹ and R ⁴² which are hydrocarbon groups are bonded to each other to form a ring.

In general formula (1) -4C, R ⁰⁴² is a nitrogen-containing ring. That is, in General Formula (1) -4C, R ⁰⁴² represents two nitrogen atoms other than the nitrogen atom bonded to the carbon atom of the carbonyl group among the three nitrogen atoms described in the general formula. It is a ring structure (nitrogen-containing cyclic group) having an atom and one carbon atom located between these two nitrogen atoms as a constituent atom of the ring skeleton. R ⁰⁴² may be either monocyclic or polycyclic, and is usually an aliphatic nitrogen-containing ring.
Compound (1) -4C is a compound (1) -4 in which R ⁴² and R ⁴³ which are hydrocarbon groups are bonded to each other to form a ring.

In general formula (1) -4D, R ⁰⁴³ is a nitrogen-containing ring. That is, in the general formula (1) -4D, R ⁰⁴³ represents a nitrogen atom bonded to the carbon atom of the carbonyl group among the three nitrogen atoms described in the general formula, and R ⁴¹ ′ and A ring structure (nitrogen-containing cyclic group) in which a nitrogen atom to which R ⁴² ′ is bonded together and a nitrogen atom not corresponding to any of them is a constituent atom of the ring skeleton. R ⁰⁴³ may be monocyclic or polycyclic, and may be either an aliphatic nitrogen-containing ring or an aromatic nitrogen-containing ring.
Compound (1) -4D is a compound (1) -4 in which R ⁴³ and R ⁴⁴ which are hydrocarbon groups are bonded to each other to form a ring.

In General Formula (1) -4E, R ⁰⁴¹ and R ⁰⁴³ are nitrogen-containing rings, R ⁰⁴¹ is the same as R ⁰⁴¹ in General Formula (1) -4B, and R ⁰⁴³ is General Formula (1) -4D. The same as R ^{043 in the} middle.
In compound (1) -4E, among compounds (1) -4, R ⁴¹ and R ⁴² which are hydrocarbon groups are bonded to each other to form a ring, and R ⁴³ and R ⁴⁴ which are hydrocarbon groups are mutually bonded. To form a ring.

Preferred examples of compound (1) -4A include those in which R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ are all alkyl groups or aryl groups.
Preferred examples of compound (1) -4B include those wherein R ⁰⁴¹ is an aliphatic nitrogen-containing ring.
Preferred examples of compound (1) -4D include those in which R ⁰⁴³ is an aliphatic nitrogen-containing ring.
Preferred examples of compound (1) -4E include those wherein R ⁰⁴¹ and R ⁰⁴³ are aliphatic nitrogen-containing rings.

  More preferable compound (1) -4 is an alkyl having 1 to 5 carbon atoms in which the following compounds and one or more hydrogen atoms bonded to the carbon atoms constituting the nitrogen-containing ring skeleton of these compounds are bonded. And those substituted with a group. Here, the “nitrogen-containing ring skeleton” constitutes X in the general formula (1).

（式中、ｎ_１、Ｚ^１、Ｒ^４１’、Ｒ^４２’、Ｒ^４３’及びＲ^４４’は前記と同じである。）

(In the formula, n ₁ , Z ¹ , R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ are the same as described above.)

  In addition, compound (1) -1, compound (1) -2, compound (1) -3, and compound (1) -4 are only some examples of compound (1), and compound (1) is It is not limited to these.

  Among the compounds (1), more preferred are compound (1) -1A, compound (1) -2E, compound (1) -3A and compound (1) -4A.

（式中、Ｇ、Ｒ^１１’、Ｒ^１２’、Ｒ^１３’、Ｒ^０２１、Ｒ^０２３、Ｒ^３１’、Ｒ^３２’、Ｒ^３３’、Ｒ^４１’、Ｒ^４２’、Ｒ^４３’及びＲ^４４’は、前記と同じである。）

(Wherein G, R ¹¹ ′, R ¹² ′, R ¹³ ′, R ⁰²¹ , R ⁰²³ , R ³¹ ′, R ³² ′, R ³³ ′, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ 'Is the same as above.)

  Among the compounds (1), compounds (1) -1A-1, compounds (1) -1A-2, compounds (1) -1A-3, compounds (1) -2E-1, and compounds are particularly preferable. (1) A compound in which one or more hydrogen atoms bonded to carbon atoms constituting the nitrogen-containing ring skeleton of -2E-1 are substituted with an alkyl group having 1 to 5 carbon atoms, Compound (1) -3A- 1, compound (1) -4A-1.

（式中、ｎ_１、Ｚ^１、Ｒ^１１’、Ｒ^１２’、Ｒ^３１’、Ｒ^３２’、Ｒ^３３’、Ｒ^４１’、Ｒ^４２’、Ｒ^４３’及びＲ^４４’は、前記と同じである。）

(In the formula, n ₁ , Z ¹ , R ¹¹ ′, R ¹² ′, R ³¹ ′, R ³² ′, R ³³ ′, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ are the same as described above. .)

<Method for Producing Compound (1)>
Compound (1) can be produced, for example, using a technique for forming an amide bond.
As a method for producing such a compound (1), for example, a compound represented by the following general formula (1a) (hereinafter sometimes abbreviated as “compound (1a)”) and the following general formula (1b): (Hereinafter sometimes abbreviated as “compound (1b)”) to obtain compound (1) (hereinafter abbreviated as “compound (1) production step”). There is a production method having

（式中、Ｇ及びＸは前記と同じであり；Ｌはハロゲン原子である。）

(In the formula, G and X are the same as above; L is a halogen atom.)

In general formula (1a), G is the same as G in general formula (1).
In general formula (1a), L is a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.
In general formula (1b), X is the same as X in general formula (1).

In the production step of compound (1), compound (1a) and compound (1b) are reacted.
During the reaction, the compound (1b) is preferably used in an amount of 1 to 5 times, more preferably 1 to 3 times the amount of the compound (1a).

The reaction of compound (1a) and compound (1b) is preferably carried out using a solvent.
The said solvent is not specifically limited, What is necessary is just to select suitably according to the kind of compound (1a) and compound (1b). Preferred examples of the solvent include ethers such as tetrahydrofuran (THF); ketones such as acetone and methyl ethyl ketone (MEK).
The solvent may be used, for example, by mixing with any component other than the solvent such as compound (1a) and compound (1b) and dissolving or dispersing this component in advance. You may use it by mixing a solvent with these components, without melt | dissolving or disperse | distributing any components other than these beforehand.

  A solvent may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  Although the usage-amount of the solvent at the time of reaction is not specifically limited, For example, it is preferable that it is 1-100 mass times with respect to the total usage-amount of a compound (1a) and a compound (1b), and is 2-60 mass times. More preferably.

For example, when a salt such as hydrochloride of compound (1b) is used instead of compound (1b), it is preferable to carry out reaction with compound (1a) using the salt of compound (1b) and a base. . By using the base in this way, the reaction proceeds more smoothly.
The base may be either an organic base or an inorganic base. For example, examples of the inorganic base include sodium hydroxide and potassium hydroxide.

  The bases may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.

  During the reaction, the amount of the base used is preferably 1 to 4 times the molar amount, and more preferably 1 to 3 times the molar amount of the salt used of the compound (1b).

  The temperature during the reaction between the compound (1a) and the compound (1b) may be appropriately adjusted in consideration of other reaction conditions, and is not particularly limited, but is preferably −5 to 35 ° C., −2 to More preferably, it is 30 ° C.

  The reaction time of the compound (1a) and the compound (1b) may be appropriately adjusted in consideration of other reaction conditions, and is not particularly limited, but is preferably 0.5 to 24 hours, and 1 to 12 hours. It is more preferable that

  The reaction between the compound (1a) and the compound (1b) is preferably carried out by reducing the amount of water in the reaction system. For example, the reaction is carried out using a dry solvent, nitrogen gas, argon gas, helium gas, etc. It is preferable to carry out the reaction in an inert gas atmosphere.

In addition, as a compound (1a), a commercial item may be used and what was obtained by manufacturing by a well-known method may be used.
Among the compounds (1a), those in which L is a chlorine atom include, for example, compounds in which X in the general formula (1a) is substituted with a hydroxyl group (—OH) (that is, the general formula “GC (═O ) -OH (wherein G is as defined above) "is converted to thionyl chloride (SOCl ₂ ), sulfuryl chloride (SO ₂ Cl ₂ ), phosphoryl chloride (POCl ₃ ), oxalyl chloride ( It can be obtained by reacting with any chlorinating agent such as (COCl) ₂ ), phosphorus trichloride (PCl ₃ ) or phosphorus pentachloride (PCl ₅ ).

In the production step of compound (1), after completion of the reaction, the compound (1) may be taken out by performing post-treatment as necessary by a known method. That is, as needed, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, concentration, etc. are performed alone or in combination of two or more, and concentration, crystallization, reprecipitation, column chromatography are performed. The compound (1) may be taken out by, for example. In addition, the taken out compound (1) is further subjected to operations such as crystallization, reprecipitation, column chromatography, extraction, stirring and washing of crystals with a solvent, if necessary, or a combination of two or more. You may refine | purify by performing it more than once.
In the production step of compound (1), after completion of the reaction, compound (1) may be used for the intended purpose without taking out compound (1).

  Here, the case where the compound (1b) is reacted with the compound (1a) has been described. For example, the compound (1b) having a group represented by the formula “—NH—” or the like (1a) In the case where a reaction other than the target is likely to proceed during the reaction with), the compound (1a) is reacted after introducing a protecting group into the corresponding group, and deprotection is carried out after this reaction. (1) may be obtained. Thus, the compound (1) can be easily produced by adding or changing a part of the steps in the production method described above.

  Moreover, although the manufacturing method which has the above-mentioned compound (1) manufacturing process was demonstrated as a manufacturing method of a compound (1) here, the combination of other raw material compounds other than a compound (1a) and a compound (1b) was used. Thus, compound (1) may be produced. For example, instead of the compound (1a), a compound represented by the general formula “GC (═O) —OH (wherein G is as defined above)” is used, and the compound (1b) is used. Instead, a compound represented by the general formula “XC (═O) —X (wherein X is the same as described above, and two Xs may be the same as or different from each other)” is used. The compound (1) can also be obtained by reacting these compounds.

  Moreover, although the manufacturing method which has the above-mentioned compound (1) manufacturing process was demonstrated as a manufacturing method of a compound (1) here, it is not the method of forming an amide bond, Other than a compound (1a) and a compound (1b) Compound (1) may be produced by forming a different bond using a combination of other raw material compounds.

  The structure of the compound (1) can be confirmed by a known method such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR) and the like.

  Compound (1) is useful as a base conversion proliferating agent described later.

<Base conversion growth agent>
The base conversion proliferating agent of the present invention comprises a compound represented by the following general formula (1), and generates a new base by the action of a base and an epoxy compound having an epoxy group. A new base is also generated by the action of the prepared base and the epoxy compound.
That is, the base conversion proliferating agent of the present invention comprises compound (1), but in this case, 1,1′-carbonyldiimidazole, which is a known compound, is not excluded from compound (1). Base conversion growth agents comprising 1,1′-carbonyldiimidazole are included in the base conversion growth agent of the present invention.

（式中、Ｇは有機基であり（ただし、ホルミルアリール基を除く）；Ｘは下記一般式（１）−１１、（１）−１２、（１）−１３又は（１）−１４で表される基である。）

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に水素原子又は炭化水素基であり、Ｒ^１１、Ｒ^１２及びＲ^１３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^３１、Ｒ^３２及びＲ^３３のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４のうちの２種以上が炭化水素基である場合、これら炭化水素基は相互に結合して環を形成していてもよく；符号＊を付した結合は、Ｘの結合先である炭素原子に対して形成されている。）

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.)

  Compound (1) functions as a base conversion proliferator regardless of the number of epoxy groups possessed by one molecule of epoxy compound. However, in order for the photocurable composition described later to be curable, an epoxy compound having two or more epoxy groups in one molecule is an essential component in the photocurable composition.

The base conversion proliferating agent is presumed to act as follows.
That is, a photobase generator that generates a base upon exposure (sometimes simply referred to as “photobase generator” in this specification) is a base represented by the following general formula (9) -1 by exposure ( Hereinafter, when “base (9) -1”) is generated, this base (9) -1 is converted into an epoxy compound represented by the following general formula (9) -2 (hereinafter referred to as “epoxy compound (9)”). -2 ") to produce a compound represented by the following general formula (9) -3. This compound is further converted into an anionic compound (hereinafter referred to as “anionic compound (9) -3”) by the action of the base (9) -1 so that the hydroxyl group (—OH) becomes an anion (—O ⁻ ). . This anionic compound (9) -3 acts on the compound (1) which is a base conversion proliferating agent to decompose the compound (1) to newly generate the compound (1b) as a base, and the following general formula The compound represented by (9) -4 (hereinafter referred to as “compound (9) -4”) is produced. The generated base (compound (1b)) further acts on the epoxy compound (9) -2 to produce an anionic compound represented by the following general formula (9) -5 (hereinafter referred to as “anionic compound (9) — 5 ”). A part of this anionic compound (9) -5 further acts on the epoxy compound (9) -2 and finally becomes a cured product, and a part further acts on the compound (1). A new base is generated from the base conversion growth agent.
As described above, the base conversion proliferating agent of the present invention has a base conversion effect of generating a base separately by the action of a base and a base growth effect of generating a base in a self-proliferating manner. Such a base conversion proliferation action has never been disclosed so far.
It is X that mainly affects the magnitude of such action in the base conversion proliferating agent of the present invention, and the influence of G on such action is negligible or negligible.

（式中、Ｒ^９１、Ｒ^９２及びＲ^９３は、それぞれ独立に有機基である。）

(In the formula, R ⁹¹ , R ⁹² and R ⁹³ are each independently an organic group.)

On the other hand, “J. F. Cameron, J. M. J. Frechet, J. Am. Chem. Soc. 1991, 113, 4303” (Patent Document 1), “M. Shirai, M. Tsunooka” , Prog. Polym. Sci. 1996, 21, 1. "(Patent Document 2)," K. Arimitsu, R. Endo, Chem. Mater. 2013, 25, 4461-4463. "(Patent Document 3) The conventional photobase generator disclosed in ( ₂ ) generates not only a base but also carbon dioxide (CO ₂ ) by decomposition due to exposure.
In contrast, as described above, the base conversion proliferating agent of the present invention generates a base when decomposed by the action of an anionic compound, but does not generate carbon dioxide. Residues are incorporated inside the cured product. That is, the base conversion proliferating agent of the present invention has an advantage that it does not generate carbon dioxide or other unnecessary decomposition products in expressing its action. Such an excellent effect of the base conversion proliferating agent has not been disclosed at all.

<Photocurable composition>
The photocurable composition of the present invention includes an epoxy compound having two or more epoxy groups in one molecule (in this specification, sometimes simply referred to as “epoxy compound”), a photobase that generates a base upon exposure. By the action of the generator and the base generated from the photobase generator by exposure and the epoxy compound, a new base is generated, and by the action of the newly generated base and the epoxy compound Also contains a base conversion growth agent that newly generates a base.

[Epoxy compound]
The said epoxy compound in the photocurable composition of this invention will not be specifically limited if it has 2 or more of epoxy groups in 1 molecule, According to the objective, it can select arbitrarily.
For example, the epoxy compound may be any of a monomer, an oligomer, and a polymer, or may be any of a low molecular compound and a high molecular compound.

  As for the epoxy compound which the said photocurable composition contains, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be set arbitrarily.

[Photobase generator]
The photobase generator in the photocurable composition of the present invention may be a known one and is not particularly limited.
Preferable examples of the photobase generator include those that generate a base by irradiation (exposure) with light having a wavelength of 1 to 400 nm.
For example, a nonionic photobase generator that generates primary amines or secondary amines upon exposure, and a guanidine-type strong base that is generated by exposure, as disclosed in documents such as Patent Documents 1 to 3 above. The nonionic photobase generator to be used can be used in the photocurable composition of the present invention.

  As for the photobase generator which the said photocurable composition contains, only 1 type may be sufficient and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be set arbitrarily.

  In the photocurable composition, the content of the photobase generator is preferably 4 to 35% by mass, more preferably 8 to 30% by mass, based on the content of the epoxy compound. It is especially preferable that it is -25 mass%. When the content of the photobase generator is not less than the lower limit, curing of the photocurable composition proceeds more easily. Moreover, the excessive use of a photobase generator is suppressed because the said content of a photobase generator is below the said upper limit.

[Base conversion growth agent]
The base conversion proliferating agent in the photocurable composition of the present invention is not particularly limited as long as it has the above properties, but the compound (1) is preferred.
The photocurable composition of the present invention is a completely new composition that has not been heretofore present in that it contains the base conversion growth agent.

  Only 1 type may be sufficient as the base conversion growth agent which the said photocurable composition contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be set arbitrarily.

  In the photocurable composition, the content of the base conversion growth agent is preferably 3 to 15% by mass, more preferably 4 to 12% by mass, with respect to the content of the epoxy compound. It is particularly preferably 10 to 10% by mass, for example, 6 to 10% by mass, 7 to 10% by mass, etc., but these are examples. When the content of the base conversion proliferating agent is equal to or more than the lower limit value, the effect obtained by using the base conversion proliferating agent is more remarkably obtained. Moreover, the excessive use of a base conversion growth agent is suppressed because the said content of a base conversion growth agent is below the said upper limit.

[Other ingredients]
The photocurable composition of the present invention may further contain other components in addition to the epoxy compound, photobase generator and base conversion growth agent.
The other components are not particularly limited as long as the effects of the present invention are not impaired, and can be arbitrarily selected according to the purpose.
The said other component which a photocurable composition contains may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be set arbitrarily.
Preferred examples of the other components include an epoxy compound having only one epoxy group in one molecule, a sensitizer, a filler, a pigment, and a solvent. In addition, in this specification, description with a mere "epoxy compound" shall mean the "epoxy compound which has 2 or more of epoxy groups in 1 molecule" demonstrated previously unless there is particular notice.

(Epoxy compound having only one epoxy group in one molecule)
The curable composition may be capable of adjusting properties such as viscosity by containing an epoxy compound having only one epoxy group in one molecule.
Such an epoxy compound in the photocurable composition of the present invention is not particularly limited as long as it has only one epoxy group in one molecule, and can be arbitrarily selected according to the purpose.
The epoxy compound having only one epoxy group in one molecule may be, for example, any of a monomer, an oligomer and a polymer, or any of a low molecular compound and a high molecular compound.
The epoxy compound having only one epoxy group in one molecule contained in the photocurable composition may be only one kind, two kinds or more, and when there are two kinds or more, combinations and ratios thereof. Can be set arbitrarily.
The content of the epoxy compound having only one epoxy group in one molecule of the photocurable composition is not particularly limited. For example, the content of the epoxy compound having two or more epoxy groups in one molecule is used. Accordingly, it may be adjusted as appropriate.

(Sensitizer)
The curable composition can be cured by irradiation with light in a wider wavelength range by containing a sensitizer (photosensitizer). For example, as the photobase generator, those that generate a base by irradiation with ultraviolet rays (ultraviolet light) having a wavelength of 1 to 400 nm are generally used. Therefore, when such a photobase generator is used, the curable composition can be cured even by irradiation with visible light having a longer wavelength than ultraviolet rays by using a sensitizer together. In this case, the sensitizer excited by absorbing visible light or the like acts on the photobase generator, so that a base is generated from the photobase generator as in the case where the sensitizer is not used.
The sensitizer may be a known sensitizer such as benzophenone, and is not particularly limited.
Only one type of sensitizer contained in the photocurable composition may be used, or two or more types thereof may be used, and when there are two or more types, the combination and ratio thereof can be arbitrarily set. However, one kind is usually sufficient.
The content of the sensitizer in the photocurable composition is not particularly limited, and may be adjusted as appropriate.

(Filler)
By containing a filler (filler), the said curable composition can adjust characteristics, such as the viscosity of curable composition itself, and the intensity | strength of hardened | cured material, for example.
The filler may be a known material and is not particularly limited. For example, the filler may be any of a fibrous shape, a plate shape, and a granular shape, and the shape, size, and material may be appropriately selected according to the purpose.
As for the filler which a photocurable composition contains, only 1 type may be sufficient, and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be set arbitrarily.
Content of the filler of a photocurable composition is not specifically limited, What is necessary is just to adjust suitably according to the objective.

(Pigment)
The said curable composition can adjust light transmittance etc., for example by containing a pigment.
The pigment contained in the curable composition may be a known pigment, for example, any pigment such as white, blue, red, yellow, and green, and is not particularly limited.
Only 1 type may be sufficient as the pigment which a photocurable composition contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be set arbitrarily.
The pigment content of the photocurable composition is not particularly limited, and may be appropriately adjusted according to the purpose.

(solvent)
When the curable composition contains a solvent, handleability is improved.
The solvent is not particularly limited, and may be appropriately selected in consideration of the solubility and stability of the epoxy compound, photobase generator and base conversion growth agent.
Preferred examples of the solvent include halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene, o-xylene, m-xylene and p-xylene; aliphatic hydrocarbons such as hexane, heptane and octane. Carboxylic acid esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF) and 1,2-dimethoxyethane (dimethyl cellosolve); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone and cyclopentanone; Nitriles such as acetonitrile; amides such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide, and the like, are not limited thereto.

  The solvent which the said photocurable composition contains may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be set arbitrarily.

  In the photocurable composition, the content of the solvent is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and particularly preferably 40 to 70% by mass. When the content of the solvent is in such a range, the handleability of the photocurable composition is further improved.

  The said photocurable composition is obtained by mix | blending the said epoxy compound, a photobase generator, a base conversion growth agent, and another component as needed. After blending each component, the resulting product may be used as it is as a photocurable composition, or a product obtained by performing a known purification operation or the like as necessary may be used as a photocurable composition.

At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being sequentially added, or all components may be mixed while being sequentially added. Good.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer or the like; a method of adding ultrasonic waves and mixing. .

The temperature at the time of blending is not particularly limited as long as each blending component does not deteriorate, and can be set to 3 to 30 ° C., for example.
The blending time is not particularly limited as long as each blending component does not deteriorate, and can be, for example, 0.5 to 1 hour.
However, these blending conditions are only examples.

  When a composition layer such as a coating layer is formed with a conventional photocurable composition disclosed in documents such as the above-mentioned Patent Documents 1 to 3 and exposed, the deeper the composition layer, in other words, The farther the distance from the surface of the composition layer is, the harder it is to reach the light. Therefore, in the composition layer, the surface and a shallow region in the vicinity thereof are easily exposed, but are not easily exposed in the deep portion. That is, when a conventional photocurable composition is used, when the composition layer is formed thick, the photobase generator is decomposed by exposure mainly due to the surface of the composition layer and a shallow region in the vicinity thereof. In the deep part, the base is hardly generated and the curing hardly or not proceeds at all.

  On the other hand, since the photocurable composition of the present invention contains the base conversion growth agent, even when the composition layer is formed thick, the above-described curing failure is suppressed. The In the composition layer, when the surface and a shallow region in the vicinity thereof are exposed, as described above, the base is chained to the unexposed deep portion by the action of the base conversion growth agent. This is because, even if the composition layer is formed thick, it is easy to cure in the deep part. Thus, the excellent effect by the photocurable composition of the present invention that the curability is high has not been disclosed so far.

<Hardened product>
A cured product is obtained by exposing the photocurable composition of the present invention to light. That is, the manufacturing method of the hardened | cured material using the photocurable composition of this invention has the process of exposing the said photocurable composition.
The shape of the cured product can be arbitrarily selected according to the purpose, such as a film shape or a linear shape.

The photocurable composition may be attached to the target by a known method, and prebaked (dried) as necessary, and then cured.
For example, when producing a film-like cured product (cured film), an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, By applying a photocurable composition to a target product using various coaters such as a Mayer bar coater or kiss coater, or an applicator, or by immersing the target product in a photocurable composition The photocurable composition may be attached to the object.
For example, when manufacturing a film or linear cured product (cured film), screen printing method, flexographic printing method, offset printing method, ink jet printing method, dispenser printing method, jet dispenser printing method, gravure What is necessary is just to make a photocurable composition adhere to a target object using printing means, such as a printing method, a gravure offset printing method, and a pad printing method.

  Prebaking can be performed, for example, preferably at 50 to 80 ° C. for 1 to 10 minutes, but the conditions are not limited thereto.

The wavelength of light during exposure of the photocurable composition is preferably, for example, 200 to 500 nm.
Moreover, it is preferable that the illumination intensity of the light at the time of exposure is 30-100 mW / cm < ² >, for example, and it is preferable that the exposure amount is 800-8000 mJ / cm < ² >, for example.
However, the exposure conditions listed here are merely examples, and the exposure conditions of the photocurable composition are not limited to these.

The cured product obtained by exposure of the photocurable composition may be further subjected to post-baking (post-exposure heat treatment).
The post-baking can be performed, for example, preferably under conditions of 100 to 160 ° C. and 0.5 to 2 hours, but the conditions are not limited thereto.

  The thickness of the cured product of the photocurable composition may be appropriately set depending on the purpose, and is not particularly limited. However, as described above, the photocurable composition of the present invention is remarkable in that the excellent effect of high curability in a deep part away from the surface of the composition layer is remarkable even if the composition layer is thick. The thickness of the cured product is preferably 1 to 500 μm, more preferably 5 to 200 μm. In order to form a cured product having such a thickness, the thickness of the composition layer may be set in the same range.

  The cured product of the photocurable composition can have a pencil hardness of 5B or more, for example, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, etc. The cured product having any pencil hardness can be obtained. Here, “pencil hardness” means that measured according to JIS K5600-5-4.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
In the following, for example, the “compound represented by the formula (1) -1A-101” is referred to as “compound (1) -1A-101”, and the like, using the reference numerals attached to each compound, The name of the compound was established.

<Production of Compound (1)>
[Example 1]
As shown below, compound (1) -1A-101 was produced by reacting compound (1a) with compound (1b).
That is, imidazole (1.4 g, 20 mmol) was dissolved in dry tetrahydrofuran (THF) (20 mL). Separately, 4-methoxybenzoyl chloride (1.7 g, 10 mmol) was dissolved in dry tetrahydrofuran (THF) (10 mL).
Next, while the THF solution of imidazole obtained above was cooled in an ice bath, the THF solution of 4-methoxybenzoyl chloride obtained above was added dropwise thereto, and after completion of the dropwise addition, the resulting mixture was allowed to cool to room temperature. The reaction was carried out by stirring for 2 hours.
Next, methylene chloride was added to the obtained reaction solution, a saturated aqueous sodium chloride solution was further added, the mixture was stirred at room temperature, and then the aqueous layer was removed to wash the reaction solution. Further, washing of the reaction solution with the same saturated sodium chloride aqueous solution was repeated four times, and then the organic layer was concentrated to obtain the target compound (1) -1A-101 as a pale yellow solid ( (Yield 1.0g, Yield 50%)
Table 1 shows the analysis result of the obtained compound (1) -1A-101 by ¹ H-NMR.

[Example 2]
As shown below, compound (1) -4A-101 was produced by reacting compound (1a) with compound (1b).
That is, 1,1,3,3-tetramethylguanidine (2.3 g, 20 mmol) was dissolved in dry THF (20 mL). Separately, 4-methoxybenzoyl chloride (1.7 g, 10 mmol) was dissolved in dry THF (10 mL).
Next, while the THF solution of 1,1,3,3-tetramethylguanidine obtained above was cooled in an ice bath, the THF solution of 4-methoxybenzoyl chloride obtained above was added dropwise thereto. After completion, the resulting mixture was stirred at room temperature for 5 hours to carry out the reaction.
Next, chloroform was added to the obtained reaction solution and filtered, and then the filtrate was concentrated. Further, benzene was added to the obtained concentrate and filtered, and then the filtrate was concentrated, Compound (1) -4A-101 was obtained as a pale yellow solid (yield 1.6 g, yield 65%)
Table 2 shows the results of ¹ H-NMR analysis of the obtained compound (1) -4A-101.

[Example 3]
As shown below, Compound (1) -3A-101 was produced by reacting Compound (1a) with Compound (1b).
That is, acetamidine hydrochloride (0.95 g, 10 mmol) was dissolved in dry acetone (100 mL), 2N aqueous sodium hydroxide solution (10 mL) was added thereto, and the mixture was stirred at 0 ° C. for 10 minutes. An acetamidine solution was obtained. Separately, 4-methoxybenzoyl chloride (1.7 g, 10 mmol) was dissolved in dry acetone (40 mL).
Next, while cooling the acetamidine solution obtained above with an ice bath, the acetone solution of 4-methoxybenzoyl chloride obtained above was added dropwise thereto. After completion of the dropwise addition, the resulting mixture was cooled to 0 ° C. The reaction was carried out by stirring for 3 hours.
Next, methylene chloride was added to the obtained reaction solution, a saturated aqueous sodium chloride solution was further added, the mixture was stirred at room temperature, and then the aqueous layer was removed to wash the reaction solution. Further, after washing the reaction solution with the same saturated sodium chloride aqueous solution four times repeatedly, the organic layer was concentrated to obtain the target compound (1) -3A-101 as a pale yellow solid ( (Yield 1.2g, Yield 65%)
Table 3 shows the results of ¹ H-NMR analysis of the obtained compound (1) -3A-101.

[Example 4]
As shown below, compound (1) -2E-101 was produced by reacting compound (1a) with compound (1b).
That is, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) (2.8 g, 20 mmol) was dissolved in dry THF (40 mL). Separately, 4-methoxybenzoyl chloride (1.7 g, 10 mmol) was dissolved in dry THF (10 mL).
Next, while the THF solution of TBD obtained above was cooled in an ice bath, the THF solution of 4-methoxybenzoyl chloride obtained above was added dropwise thereto, and after completion of the dropwise addition, the resulting mixture was allowed to cool to room temperature. The reaction was carried out by stirring for 1.5 hours.
Next, methylene chloride was added to the obtained reaction solution, a saturated aqueous sodium chloride solution was further added, the mixture was stirred at room temperature, and then the aqueous layer was removed to wash the reaction solution. Further, washing of the reaction solution with the same saturated sodium chloride aqueous solution was repeated four times, and then the organic layer was concentrated to obtain the target compound (1) -2E-101 as a white solid (yield) 1.2g, 42% yield)
Table 4 shows the analysis result of the obtained compound (1) -2E-101 by ¹ H-NMR.

[Example 5]
Compound (1) -1A-201 was produced as shown below.
That is, carbonyldiimidazole (2.5 g, 15 mmol) was dissolved in dry THF (50 mL). Separately, 4-nitrobenzoic acid (1.9 g, 11 mmol) was dissolved in dry THF (25 mL).
Subsequently, the THF solution of 4-nitrobenzoic acid obtained above is dropped into the THF solution of carbonyldiimidazole obtained above at room temperature, and after completion of the dropwise addition, the obtained mixture is heated to reflux. The reaction was carried out by stirring for 3.5 hours.
Then, triethylamine (2.0 g, 20 mmol) was added to the reaction solution, and the reaction solution was further stirred at room temperature for 5 h.
Next, the obtained reaction solution was concentrated to remove THF and unreacted triethylamine, methylene chloride was added to the obtained concentrate, and a saturated aqueous sodium chloride solution was further added, followed by stirring at room temperature. Then, the reaction solution was washed by removing the aqueous layer. Further, washing of the reaction solution with the same saturated sodium chloride aqueous solution was repeated four times, and then the organic layer was concentrated to obtain the target compound (1) -1A-201 as a pale yellow solid ( (Yield 2.2g, Yield 90%)
Table 5 shows the analysis results of the obtained compound (1) -1A-201 by ¹ H-NMR.

<Manufacture of a photocurable composition and a cured film>
[Example 6]
(Production of photocurable composition)
Epoxy compound represented by the following formula (9) -201 (0.30 g), photobase generator represented by the following formula (8) -101 (0.06 g, 20% by mass with respect to the mass of the epoxy compound) ), Compound (1) -1A-101 (0.023 g, 7.7 mass% with respect to the mass of the epoxy compound), and chloroform (0.60 g), and stirred at 25 ° C. for 1 minute. A photocurable composition was obtained.

(Manufacture of cured film)
Using the applicator, the photocurable composition obtained above was coated on a glass substrate. Next, the coating film (composition layer) was heated (prebaked) at 60 ° C. for 3 minutes, and then an ultraviolet ray having a wavelength of 365 nm was applied using an LED lamp under the conditions of an illuminance of 50 mW / cm ² and an exposure amount of 5000 mJ / cm ^2. The film was cured by irradiation. Next, the cured coating film was heated at 140 ° C. for 60 minutes to obtain a cured film having a thickness of 50 μm.
It was 2H as a result of measuring pencil hardness about the obtained cured film based on JISK5600-5-4. The results are shown in Table 6.

[Example 7]
The amount of compound (1) -1A-101 is changed to 0.023 g (7.7% by mass with respect to the mass of the epoxy compound) instead of 0.015 g (5.1% by mass with respect to the mass of the epoxy compound). The photocurable composition was manufactured by the same method as Example 6 except the point made into), and the cured film was manufactured.
It was 4B as a result of measuring pencil hardness about the obtained cured film based on JISK5600-5-4. The results are shown in Table 6.

[Example 8]
Except that the 3000 mJ / cm ² instead of the exposure amount to 5000 mJ / cm ² was produced a cured film in the same manner as in Example 6.
It was F as a result of measuring pencil hardness about the obtained cured film based on JISK5600-5-4. The results are shown in Table 6.

[Example 9]
The amount of compound (1) -1A-101 is changed to 0.023 g (7.7% by mass with respect to the mass of the epoxy compound) instead of 0.015 g (5.1% by mass with respect to the mass of the epoxy compound). ) and the except, to produce a photocurable composition in the same manner as in example 6, the exposure amount except that the 3000 mJ / cm ² instead of 5000 mJ / cm ^2, in the same manner as in example 6 A cured film was produced.
It was 5B as a result of measuring pencil hardness about the obtained cured film based on JISK5600-5-4. The results are shown in Table 6.

[Example 10]
Except that the 1000 mJ / cm ² instead of the exposure amount to 5000 mJ / cm ² was produced a cured film in the same manner as in Example 6.
It was B as a result of measuring pencil hardness about the obtained cured film based on JISK5600-5-4. The results are shown in Table 6.

As is clear from the above results, the photocurable composition obtained using Compound (1) -1A-101 formed a film-like cured product having sufficient pencil hardness by exposure.
In addition, it replaces with 0.023g (7.6 mass% with respect to the mass of the said epoxy compound) and the compounding quantity of compound (1) -1A-101 is 0.008g (2.5 with respect to the mass of the said epoxy compound). The photocurable composition was produced by the same method as in Example 6 except that the mass%) was used, and this photocurable composition was used in the same method as in Example 6 (exposure amount 5000 mJ / cm ² ). If to produce a cured film, except that the 3000 mJ / cm ² instead of 5000 mJ / cm ² exposure amount, if you produce a cured film in the same manner as in example 6, and the exposure amount 5000 mJ / cm ² In the case where a cured film was produced by the same method as in Example 6 except that 1000 mJ / cm ² was used instead, a cured film having sufficient pencil hardness was not obtained.

[Test Example 1]
Compound (1) -1A-101 (0.05 g, 0.29 mmol), TBD (0.29 mmol), and 2-propanol (5 mL) were added to the flask, heated under reflux for 30 minutes, and then the solvent Was distilled off. The obtained solid was analyzed by ¹ H-NMR.
Furthermore, the obtained solid was analyzed by ¹ H-NMR in the same manner as described above except that TBD was not used.
The results of these analyzes are shown in FIG.

As shown in FIG. 1, the signal pattern of ¹ H-NMR was different depending on whether or not TBD was used. Then, the signal pattern using the TBD is an anion generated from 2-propanol by ^{_{TBD (CH 3 -CH (-O -}} ) -CH 3) and the compound (1) and -1A-101, the reaction product The presence of a compound considered to be a product was indicated. Each ¹ H-NMR signal with a circled numerical value can be assigned as a proton signal at a position with a circled numerical value in the reaction product.

[Test Example 2]
Instead of compound (1) -1A-101 (0.05 g, 0.29 mmol), compound (1) -2E-101 (0.05 g, 0.18 mmol) was used, and the amount used when TBD was used was 0. Analysis by ¹ H-NMR was performed in the same manner as in Test Example 1, except that 0.145 mmol was used instead of .29 mmol. The analysis results are shown in FIG.

As shown in FIG. 2, the signal pattern of ¹ H-NMR was almost the same regardless of whether or not TBD was used. These signal patterns are considered to be reaction products of an anion (CH ₃ —CH (—O ⁻ ) —CH ₃ ) generated from 2-propanol by TBD and compound (1) -2E-101. The presence of the compound was indicated. Each ¹ H-NMR signal with a circled numerical value can be assigned as a proton signal at a position with a circled numerical value in the reaction product. In addition, in FIG. 2, the analysis result of compound (1) -2E-101 itself is also shown collectively.

[Test Example 3]
The same as Test Example 1 except that Compound (1) -1A-201 (0.05 g, 0.23 mmol) was used instead of Compound (1) -1A-101 (0.05 g, 0.29 mmol). The method was analyzed by ¹ H-NMR.
As a result, as in Test Example 1, a reaction product of an anion (CH ₃ —CH (—O ⁻ ) —CH ₃ ) generated from 2-propanol and compound (1) -1A-201 Data were obtained indicating the presence of possible compounds.

[Test Example 4]
The point which replaced with compound (1) -1A-101 (0.05g, 0.29mmol) and used compound (1) -1A-301 (namely, N-benzoylimidazole) (0.05g, 0.29mmol). Except for the above, analysis by ¹ H-NMR was performed in the same manner as in Test Example 1.
As a result, as in Test Example 1, the reaction product of an anion (CH ₃ —CH (—O ⁻ ) —CH ₃ ) generated from 2-propanol and compound (1) -1A-301 Data were obtained indicating the presence of possible compounds.

  The present invention can be used in all fields where curable materials are used, including the fields of electronic materials and printing materials.

Claims (6)

An epoxy compound having two or more epoxy groups in one molecule;
A photobase generator that generates a base upon exposure, and a base generated from the photobase generator upon exposure and an action of the epoxy compound to generate a new base, and the newly generated base; A photocurable composition containing a base conversion proliferating agent that newly generates a base also by the action of the epoxy compound. The photocurable composition according to claim 1, wherein the base conversion proliferating agent is a compound represented by the following general formula (1).

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.) A compound represented by the following general formula (1) (excluding 1,1′-carbonyldiimidazole).

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.) The compound of Claim 3 represented by the following general formula (1) -1A, (1) -2E, (1) -3A or (1) -4A.

(Wherein G is the same as above; R ¹¹ ′, R ¹² ′, R ¹³ ′, R ³¹ ′, R ³² ′, R ³³ ′, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴⁾ 'Is independently a hydrogen atom or a hydrocarbon group; R ⁰²¹ and R ⁰²³ are each independently a nitrogen-containing ring.) The following general formula (1) -1A-1, (1) -1A-2, (1) -1A-3, (1) -2E-1, (1) -3A-1 or (1) -4A-1 Or one or more hydrogen atoms bonded to the carbon atoms constituting the nitrogen-containing ring skeleton of the compound represented by the general formula (1) -2E-1 The compound according to claim 4, which is a compound substituted with an alkyl group.

(In the formula, n ₁ is an integer of 0 to 5; Z ¹ is an alkoxy group, an aryloxy group or a nitro group, and when n ₁ is an integer of 2 to 5, a plurality of Z ¹ are the same as each other) R ¹¹ ′, R ¹² ′, R ³¹ ′, R ³² ′, R ³³ ′, R ⁴¹ ′, R ⁴² ′, R ⁴³ ′ and R ⁴⁴ ′ may each independently represent a hydrogen atom or It is a hydrocarbon group.) It consists of a compound represented by the following general formula (1),
Base conversion that generates a new base by the action of a base and an epoxy compound having an epoxy group, and also generates a new base by the action of the newly generated base and the epoxy compound. Proliferator.

Wherein G is an organic group (excluding the formylaryl group); X is represented by the following general formula (1) -11, (1) -12, (1) -13 or (1) -14 Group.)

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently A hydrogen atom or a hydrocarbon group, and when two or more of R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; When two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ³¹ , R ³² and When two or more of R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ If more than one species is a hydrocarbon group, these hydrocarbon groups are bonded to each other And a ring may be formed; the bond marked with a symbol * is formed with respect to the carbon atom to which X is attached.)

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