JPWO2019216322A1 - Curable compositions, compounds, base conversion growth agents and cured products - Google Patents

Abstract

A curable composition containing an epoxy compound having two or more epoxy groups in one molecule and a compound represented by the following general formula (1). In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or the ester structure. A group containing a hydrocarbon group which may have a substituent, which does not have a hydrogen atom bonded to the β-position or does not have a β-position, or a nitrogen atom forming an amide structure with an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. It is a group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. Is the group to be. [Chemical 1]

Description

The present invention relates to curable compositions, compounds, base conversion growth agents and cured products.

Photocurable materials that are cured (polymerized) by irradiation with light have been widely put into practical use because the curing reaction can be precisely controlled with a relatively simple operation. For example, in the fields of electronic materials and printing materials. It occupies an important position in such cases.
Examples of the photocurable material include a radical polymerization-based photocurable composition containing a photoinitiator that generates a radical species by light irradiation and a radically polymerizable monomer or oligomer, and an acid that is generated by light irradiation. So far, 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, as a photocurable material, a base catalyst system containing a photobase generator that generates a base by light irradiation and a monomer or oligomer that is cured by the action of a base is also known. As the monomer or oligomer that is cured 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 produces a primary amine or a secondary amine by light irradiation and a nonionic photobase generator that produces a guanidine-type strong base by light irradiation are known. (See Non-Patent Documents 1 to 3).

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

In addition to the base-catalyzed photocurable compositions disclosed in Non-Patent Documents 1 to 3, it is desired to develop a novel curable composition that cures by light irradiation or heating. Further, there is a demand for a curable composition having better curability when a base generator that generates a base by light irradiation or heating is used.

An object of the present invention is to provide a novel curable composition, a compound and a base conversion growth agent used in the curable composition, and a cured product obtained by using the curable composition. do.
In addition, another embodiment of the present invention is a curable composition having better curability using a base generator that generates a base by light irradiation or heating, a compound and a base conversion growth agent used in this curable composition. , And a cured product obtained using this curable composition.

Specific means for solving the above problems are as follows.
<1> A curable composition containing an epoxy compound having two or more epoxy groups in one molecule and a compound represented by the following general formula (1).

(In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or with respect to the ester structure. A nitrogen atom that forms an amide structure with a group containing a hydrocarbon group that does not have a hydrogen atom bonded to the β-position, does not have a β-position, or may have a substituent, or an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. It is a group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. It is the group to be done.)

(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 independent of each other. When it is a hydrogen atom or a hydrocarbon group and ^{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, 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 2 of R ⁴¹ , R ⁴² , R ⁴³ and R ^44. When the species or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is formed for the carbon atom to which X is bonded. ing.)
<2> The curable composition according to <1>, further comprising a base generator that generates a base by light irradiation or heating.
<3> The compound represented by the general formula (1) includes at least one of the compound represented by the following general formula (1) -A and the compound represented by the general formula (1) -B <1>. Alternatively, the curable composition according to <2>.

(In the formula, R ¹ has a pKa of the hydrogen atom at the β-position with respect to the adjacent ester structure of 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent ester structure or the β-position does not exist. It is a hydrocarbon group which may have a substituent, and R ² and R ³ are independently hydrogen atoms or the pKa of the β-position hydrogen atom with respect to the adjacent amide structure is 27 or more, or are adjacent to each other. It is a hydrocarbon group which may have a substituent, in which a hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist, and X is independently the general formula (1) -11, ( 1) A group represented by -12, (1) -13 or (1) -14. At ^{least one of R 2} and R ³ has a pKa of the β-position hydrogen atom with respect to the adjacent amide structure of 27 or more. Alternatively, it is a hydrocarbon group that may have a substituent, with no hydrogen atom attached to the β-position or no β-position with respect to the adjacent amide structure. R ² and R ³ are adjacent amides. The pKa of the hydrogen atom at the β-position with respect to the structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent amide structure or the β-position does not exist. In the case of hydrogen groups, these hydrocarbon groups may be bonded to each other to form a ring.)
<4> When the compound represented by the general formula (1) is a compound represented by the general formula (1) -A, R ¹ contains an alkyl group or a substituent which may have a substituent. When it is an aryl group that may have and the compound represented by the general formula (1) is a compound represented by the general formula (1) -B, one of R ² and R ³ is a hydrogen atom. The curable composition according to <3>, wherein the other of R ² and R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent.

<5> A compound represented by the following general formula (1).

(In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or the ester. Nitrogen that forms an amide structure with a group containing a hydrocarbon group that may have a substituent, that does not have a hydrogen atom bonded to the β-position with respect to the structure or does not have a β-position, or an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, which is bonded to the atom and the nitrogen atom, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. , A group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. It is a group represented.)

(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 independent of each other. When it is a hydrogen atom or a hydrocarbon group and ^{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, 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 2 of R ⁴¹ , R ⁴² , R ⁴³ and R ^44. When the species or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is formed for the carbon atom to which X is bonded. ing.)
<6> The compound according to <5>, which is a compound represented by the following general formula (1) -A or a compound represented by the general formula (1) -B.

(In the formula, R ¹ has a pKa of the hydrogen atom at the β-position with respect to the adjacent ester structure of 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent ester structure or the β-position does not exist. It is a hydrocarbon group which may have a substituent, and R ² and R ³ are independently hydrogen atoms or the pKa of the β-position hydrogen atom with respect to the adjacent amide structure is 27 or more, or are adjacent to each other. It is a hydrocarbon group which may have a substituent, in which a hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist, and X is independently the general formula (1) -11, ( 1) A group represented by -12, (1) -13 or (1) -14. At ^{least one of R 2} and R ³ has a pKa of the β-position hydrogen atom with respect to the adjacent amide structure of 27 or more. Alternatively, it is a hydrocarbon group that may have a substituent, with no hydrogen atom attached to the β-position or no β-position with respect to the adjacent amide structure. R ² and R ³ are adjacent amides. The pKa of the hydrogen atom at the β-position with respect to the structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent amide structure or the β-position does not exist. In the case of hydrogen groups, these hydrocarbon groups may be bonded to each other to form a ring.)
<7> When the compound represented by the general formula (1) is a compound represented by the general formula (1) -A, R ¹ contains an alkyl group or a substituent which may have a substituent. When it is an aryl group that may have and the compound represented by the general formula (1) is a compound represented by the general formula (1) -B, one of R ² and R ³ is a hydrogen atom. The compound according to <6>, wherein the other of R ² and R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent.

<8> A new base is generated by the action of a base and an epoxy compound having an epoxy group, which contains a compound represented by the following general formula (1), and the newly generated base and the epoxy A base conversion propaganda agent that generates a new base by the action of a compound.

(In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or the ester. Nitrogen that forms an amide structure with a group containing a hydrocarbon group that may have a substituent, that does not have a hydrogen atom bonded to the β-position with respect to the structure or does not have a β-position, or an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, which is bonded to the atom and the nitrogen atom, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. , A group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. It is a group represented.)

(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 independent of each other. When it is a hydrogen atom or a hydrocarbon group and ^{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, 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 2 of R ⁴¹ , R ⁴² , R ⁴³ and R ^44. When the species or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is formed for the carbon atom to which X is bonded. ing.)

<9> A cured product obtained by reacting the curable composition according to any one of <1> to <4>.

According to one embodiment of the present invention, it is possible to provide a novel curable composition, a compound and a base conversion growth agent used in the curable composition, and a cured product obtained by using the curable composition. can.
According to another embodiment of the present invention, a curable composition having better curability, a compound and a base conversion breeding agent used in the curable composition, using a base generator that generates a base by light irradiation or heating. , And a cured product obtained using this curable composition can be provided.

It is a graph which shows the measurement result of the FT-IR spectrum in Example 6. 6 is a graph showing the relationship between the heating time and the peak area ratio due to the epoxy group in Examples 6 and 7 and Reference Examples 2 and 3. 9 is a graph showing the measurement result of the FT-IR spectrum in Example 9. 3 is a graph showing the relationship between the heating time and the peak area ratio due to the epoxy group in Examples 8 and 9 and Reference Example 4. It is a graph which shows the relationship between the heating time and the peak area ratio due to an epoxy group in Examples 10-12.

The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

<Compound (1)>
The compound of the present disclosure (hereinafter, may be referred to as “compound (1)”) is represented by the following general formula (1).

In the general formula (1), G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or , A group containing a hydrocarbon group which does not have a hydrogen atom bonded to the β-position or does not have a β-position with respect to the ester structure and may have a substituent, or an adjacent carbonyl group and an amide structure. The nitrogen atom to be formed is bonded to the nitrogen atom, and the pKa of the β-position hydrogen atom with respect to the amide structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position. Is a group containing a hydrocarbon group which may have a substituent in the absence of, and X is the following general formula (1) -11, (1) -12, (1) -13 or (1). It is a group represented by -14.

In the general formulas (1) -11 to (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 independent hydrogen atoms or hydrocarbon groups, respectively, and when ^{two or more of R 11} , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups are bonded to each other. 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 to form a ring. If ^{two or more of R 31} , R ³² and R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, R ⁴¹ , R. ^When two or more of 42, R ⁴³ and R ⁴⁴ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is of X. It is formed for the carbon atom to which it is bonded.

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

Further, the compound (1) has a base conversion action of separately generating a base by the action of a base as described later, and also has a base proliferation action of self-proliferating to generate a base. Furthermore, since compound (1) itself also acts as a base, the epoxy compound undergoes a curing reaction when mixed with an epoxy compound described later and heated.

In the general formula (1), G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or A group containing a hydrocarbon group which may have a substituent, which does not have a hydrogen atom bonded to the β-position or does not have a β-position with respect to the ester structure, or forms an amide structure with an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position is bonded to the nitrogen atom. A group containing a non-existent hydrocarbon group which may have a substituent.

When the pKa of the β-position hydrogen atom with respect to the ester structure and the amide structure is 27 or more, for example, by irradiating or heating a curable composition containing a base generator that generates a base by light irradiation or heating. When a base is generated, the reactivity between the base and the hydrogen atom at the β-position is low, so that the β-elimination reaction in which the hydrogen atom at the β-position is extracted by the base is unlikely to occur. As a result, it is possible to suppress the decomposition of a part of G in the general formula (1) to generate a decomposed product having multiple bonds, and the generation of carbon dioxide or the like derived from the ester structure, so that the curability is curable. Poor curing of the composition can be suppressed. From the viewpoint of more preferably suppressing the reaction between the above-mentioned base and the hydrogen atom at the β-position, the pKa of the hydrogen atom at the β-position with respect to the ester structure and the amide structure is preferably 30 or more independently, and is 35 or more. Is more preferable.
The pKa of the β-position hydrogen atom with respect to the ester structure and the amide structure depends on, for example, the presence or absence of a substituent, the type, position and number of substituents, the presence or absence of a conjugated structure, the type and position of the conjugated structure, etc. for the hydrocarbon group. Can be adjusted.

When a hydrogen atom is not bonded to the β-position with respect to the ester structure and the amide structure or the β-position does not exist, for example, when a base is generated by irradiating or heating a curable composition containing a base generator with light. In addition, since the hydrogen atom does not exist at the β-position or the β-position itself does not exist, the β elimination reaction due to the extraction of the hydrogen atom does not occur. As a result, it is possible to suppress the decomposition of a part of G in the general formula (1) to generate a decomposed product having multiple bonds, and the generation of carbon dioxide or the like derived from the ester structure, so that the curability is curable. Poor curing of the composition can be suppressed.
Hydrocarbon groups that may have a substituent in which a hydrogen atom is not bonded to the β-position with respect to the ester structure and the amide structure include hydrocarbons having a quaternary carbon at the β-position and one or more substitutions at the β-position. Examples thereof include hydrocarbons to which groups are bonded and hydrogen atoms are not bonded, hydrocarbons having an aromatic carbon at the β-position, and the like.
Examples of the hydrocarbon group which may have a substituent which does not have a β-position with respect to the ester structure and the amide structure include a methyl group which may have a substituent.

The compound (1) is preferably a compound represented by the following general formula (1) -A or a compound represented by the general formula (1) -B, and is excellent in thermal stability in the presence of an epoxy compound. Therefore, it is more preferable that the compound is represented by the following general formula (1) -A.

In the general formulas (1) -A and (1) -B, R ¹ has a pKa of a hydrogen atom at the β-position with respect to an adjacent ester structure of 27 or more, or a hydrogen atom at the β-position with respect to the ester structure. Is a hydrocarbon group which may have a substituent, which is not bonded or has no β-position, and R ² and R ³ are independently hydrogen atoms or β-position hydrogen atoms with respect to an adjacent amide structure. It is a hydrocarbon group having a pKa of 27 or more, or having no hydrogen atom bonded to the β-position with respect to the amide structure or having no β-position, and may have a substituent, and X is independent of each other. It is a group represented by the general formula (1) -11, (1) -12, (1) -13 or (1) -14. At ^{least one of R 2} and R ³ has a pKa of a hydrogen atom at the β-position with respect to the adjacent amide structure of 27 or more, or no hydrogen atom is bonded to the β-position with respect to the amide structure or there is no β-position. , A hydrocarbon group which may have a substituent. A ^{substituent in which the pKa of the hydrogen atom at the β-position with respect to the amide structure adjacent to R 2} and R ³ is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. When it is a hydrocarbon group which may have, these hydrocarbon groups may be bonded to each other to form a ring.

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 the hydrogen atom, or constitutes a hydrocarbon group. A group (substitution) different from that of a carbon atom or a carbon atom to which one or more hydrogen atoms are bonded, together with one or more carbon atoms to which the carbon atom is bonded, or one or more hydrogen atoms to which the carbon atom is bonded. It means that it is replaced with a group). Then, both the hydrogen atom and the carbon atom may be substituted with a substituent.

The hydrocarbon group 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. Alternatively, it may be a polycyclic hydrocarbon group formed by condensing a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.
The alkyl group may be linear, branched or cyclic, and when cyclic, it may be monocyclic or polycyclic. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 2 to 20 carbon atoms.

The linear or branched alkyl group preferably has 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. 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 Group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, Examples thereof include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, and an icosyl group.

The cyclic alkyl group preferably has 3 to 20 carbon atoms, and 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. , Cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group and the like, and further, one or more hydrogen atoms of these cyclic alkyl groups are linear or branched. Examples thereof include those substituted with a chain or cyclic alkyl group. Here, examples of the linear, branched-chain, and cyclic alkyl groups substituting hydrogen atoms include those described above as examples of alkyl groups.

The unsaturated aliphatic hydrocarbon group may be linear, branched chain 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.
As the unsaturated aliphatic hydrocarbon group, one or more single bonds (CC) between carbon atoms in the alkyl group are double bonds (C = C) or triple bonds which are unsaturated bonds. Examples thereof include groups substituted with (C≡C).
In the unsaturated aliphatic hydrocarbon group, the number of unsaturated bonds may be only one, two or more, and when two or more, these unsaturated bonds may be only double bonds or triple bonds. It may be only a bond, or a mixture of double and triple bonds.
In the unsaturated aliphatic hydrocarbon group, the position of the unsaturated bond is not particularly limited.

Preferred unsaturated aliphatic hydrocarbon groups include, for example, an alkenyl group and an alkynyl group having a linear or branched chain corresponding to one unsaturated bond, and a cyclic group. Cycloalkenyl group and cycloalkynyl group.
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 may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms. Examples of such an aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xsilyl group (dimethylphenyl group) and the like. Examples thereof include those in which one or more hydrogen atoms of these aryl groups are further substituted with these aryl groups or the alkyl group. The aryl group having these substituents preferably has 6 to 20 carbon atoms including the substituent.

Among the above-mentioned hydrocarbon groups, as the aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group (aryl group), for example, if the number of hydrogen atoms substituted is 1. , An arylalkyl group (aralkyl group) such as a phenylmethyl group (benzyl group) and a 2-phenylethyl group (phenethyl group).

Examples of the substituent in which one or more hydrogen atoms are substituted in the above 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 (alkyl halide group), hydroxyl group (-OH), mercapto group (-SH) and the like can be mentioned.

In the hydrocarbon group, the substituent for substituting a hydrogen atom may be only one, two or more, and all hydrogen atoms may be substituted with the substituent.
In the hydrocarbon group, when the number of the substituents substituting the hydrogen atom is two or more, these substituents may be all the same, all may be different, or only a part thereof may be the same. May be good.

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

As the dialkylamino group which is a substituent, for example, 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.} Can be mentioned. In the dialkylamino group, the 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 in which two hydrogen atoms of an amino group such as a diphenylamino group and a phenyl-1-naphthylamino group are substituted with the aryl group. Be done. In the diarylamino group, the two aryl groups bonded to the nitrogen atom may be the same as or different from each other.
As the alkylarylamino group which is a substituent, for example, one hydrogen atom of two hydrogen atoms of an amino group such as a methylphenylamino group is substituted with the alkyl group, and one hydrogen atom is used. Examples thereof include a monovalent group substituted with the aryl group.

Examples of the alkylcarbonyl group as a substituent include a monovalent group in which the alkyl group is bonded to a carbonyl group (-C (= O)-), such as a methylcarbonyl group (acetyl group).
Examples of the arylcarbonyl group as a substituent include a monovalent group in which the aryl group is bonded to a carbonyl group, such as a phenylcarbonyl group (benzoyl group).

Examples of the alkyloxycarbonyl group as a substituent include a monovalent group in which the alkoxy group is bonded to a carbonyl group, such as a methyloxycarbonyl group (methoxycarbonyl group).
Examples of the aryloxycarbonyl group as a substituent include a monovalent group in which the aryloxy group is bonded to a carbonyl group, such as a phenyloxycarbonyl group (phenoxycarbonyl group).

The alkylcarbonyloxy group which is a substituent is, for example, a methylcarbonyloxy group or the like, which is a monovalent group formed by bonding the alkyl group to the carbon atom of the carbonyloxy group (-C (= O) -O-). Can be mentioned.
Examples of the arylcarbonyloxy group as a substituent include a monovalent group formed by bonding the aryl group to the carbon atom of the carbonyloxy group, such as a phenylcarbonyloxy group.

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

Examples of the halogen atom as a substituent include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

Examples of the haloalkyl group as a substituent include a group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom.
Examples of the halogen atom in the haloalkyl group include those described above as examples of the halogen atom as the substituent.
The number of halogen atoms in the haloalkyl group is not particularly limited, and may be one or two or more. When the number of halogen atoms in the haloalkyl group is two or more, these plurality of halogen atoms may all be the same, all may be different, or only some of them 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, a trifluoromethyl group and the like.

In the hydrocarbon group, the number of the substituents substituting a hydrogen atom depends on the number of substitutable hydrogen atoms, but is preferably 1 to 4, more preferably 1 to 3. It is particularly preferable that the number is one or two.

In the hydrocarbon group, examples of the substituent in which one or more carbon atoms are substituted together with one or more hydrogen atoms to which the carbon atom is bonded include a nitrogen atom, an oxygen atom, and a sulfur atom. Heteroatoms such as.

In the hydrocarbon group, the substituent that replaces the carbon atom or the carbon atom to which the hydrogen atom is bonded may be only one or two or more, and all the carbon atoms are alone or the carbon atom. It may be substituted with a substituent together with the hydrogen atom bonded to.
In the hydrocarbon group, when there are two or more of the substituents substituting the carbon atom or the carbon atom to which the hydrogen atom is bonded, these substituents may all be the same or all be different. It may be the same, and only a part of it may be the same.

Among the hydrocarbon groups substituted with heteroatoms, the aromatic hydrocarbon group, that is, the aromatic heterocyclic group (heteroaryl group) is composed of various aromatic heterocyclic compounds to form a ring skeleton thereof. A group consisting of a carbon atom or a heteroatom excluding one hydrogen atom bonded to the heteroatom can be mentioned.
Preferred aromatic heterocyclic compounds are sulfur-containing aromatic heterocyclic compounds (compounds having one or more sulfur atoms as atoms constituting the aromatic heterocyclic skeleton) and nitrogen-containing aromatic heterocyclic compounds (fragrance). A compound having one or more nitrogen atoms as an atom constituting the group heterocyclic skeleton), an oxygen-containing aromatic heterocyclic compound (a compound having one or more oxygen atoms as an atom constituting the aromatic heterocyclic skeleton), sulfur Examples thereof include compounds having two different heteroatoms selected from an atom, a nitrogen atom and an oxygen atom as atoms constituting the aromatic heterocyclic skeleton.

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, benzoimidazole, purine, indazole, quinoline, isoquinolin, quinoxaline, quinazoline, and cinnoline. And so on.

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

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

In the hydrocarbon group, the number of the substituent for substituting the carbon atom or the carbon atom to which the hydrogen atom is bonded is preferably 1 to 3 or 1 or 3 depending on the substitutable carbon atom. It is more preferable that the number is two.

R ^{1 to} R ³ may each have an independently substituent, preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, or an arylalkyl group, and each of them has a substituent. It may be an alkyl group or an aryl group, more preferably an alkyl group which may have a substituent. The substituents here are the same as the above-mentioned substituents described as having the hydrocarbon group.
Further, R ¹ and R ² may each have an independently substituent, and are an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, or an arylalkyl group, and R ³ is a hydrogen atom. R ¹ and R ² may have a substituent, more preferably an alkyl group or an aryl group, and R ³ is a hydrogen atom, and R ¹ and R ² have a substituent. It is more preferably an alkyl group which may be used and R ³ is a hydrogen atom.

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

In the general formulas (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 independently hydrogen atoms or hydrocarbon groups, respectively.
That is, in the general formula (1) -11, R ¹¹ , R ¹² and R ¹³ (hereinafter, ^{may be abbreviated as "R 11 to} R ¹³ ") may all be the same or different. It may be the same, or only a part thereof may be the same.
Similarly, in the general formula (1) -12, R ²¹ , R ²² , R ²³ and R ²⁴ (hereinafter, ^{may be abbreviated as “R 21 to} R ²⁴ ”) may all 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, ^{may be abbreviated as “R 31 to} R ³³ ”) may all be the same or all different. It may be the same, or only a part of it 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 groups in R 11 to} R ¹³ , R ^{21 to} R ²⁴ , R ^{31 to} R ³³ , and R ^{41 to} R ⁴⁴ may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). It may be an aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group, or a polycyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group are fused. It may be a cyclic hydrocarbon group.

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

The alkyl group may be linear, branched or cyclic, and when 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, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. 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 Group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, Examples thereof include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, and an icosyl group.

The cyclic alkyl group preferably has 3 to 20 carbon atoms, and 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. , Cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group and the like, and further, one or more hydrogen atoms of these cyclic alkyl groups are linear or branched. Examples thereof include those substituted with a chain or cyclic alkyl group. Here, examples of the linear, branched-chain, and cyclic alkyl groups substituting hydrogen atoms include those described above as examples of alkyl groups.

The unsaturated aliphatic hydrocarbon group may be linear, branched chain 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.
As the unsaturated aliphatic hydrocarbon group, one or more single bonds (CC) between carbon atoms in the alkyl group are double bonds (C = C) or triple bonds which are unsaturated bonds. Examples thereof include groups substituted with (C≡C).
In the unsaturated aliphatic hydrocarbon group, the number of unsaturated bonds may be only one, two or more, and when two or more, these unsaturated bonds may be only double bonds or triple bonds. It may be only a bond, or a mixture of double and triple bonds.
In the unsaturated aliphatic hydrocarbon group, the position of the unsaturated bond is not particularly limited.

Preferred unsaturated aliphatic hydrocarbon groups include, for example, an alkenyl group and an alkynyl group having a linear or branched chain corresponding to one unsaturated bond, and a cyclic group. Cycloalkenyl group and cycloalkynyl group.
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 may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms. Examples of such an aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xsilyl group (dimethylphenyl group) and the like. Examples thereof include those in which one or more hydrogen atoms of these aryl groups are further substituted with these aryl groups, the alkyl group and the like. The aryl group having these substituents preferably has 6 to 20 carbon atoms including the substituent.

^{When two or more of R 11} , R ¹² and R ^{13 in} the general formula (1) -11 are hydrocarbon groups, these hydrocarbon groups are bonded to each other and these hydrocarbon groups are bonded to each other. It may form a ring together with a carbon atom (a carbon atom constituting an imidazole skeleton). Here, "two or more kinds of hydrocarbon groups are bonded to each other" means that ^{only two kinds or all (three kinds) of R 11 to} R ¹³ are hydrocarbon groups, and any two kinds of hydrocarbons are carbonized. 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 of these hydrocarbon groups are bonded to each other. In either case, these hydrocarbon groups are assumed to have carbon atoms bonded to each other.

When two or more hydrocarbon groups are bonded to each other, the position (bonding position) of the carbon atom to be bonded is not particularly limited. For example, when the hydrocarbon group to be bonded is linear or branched, the bonding position may be the carbon atom at the end of the hydrocarbon group, or constitutes the imidazole skeleton of the hydrocarbon group. It may be a so-called root carbon atom that is directly bonded to a carbon atom, or it may be a carbon atom at an intermediate position between these terminals and the root. On the other hand, when the hydrocarbon group to be bonded is cyclic or has both a chain structure and a cyclic structure, the bond position may be a carbon atom at the root or a carbon atom other than that. May be 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 fused.

In the 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 formed. A ring may be formed together with the bonded nitrogen atom and the carbon atom bonded to the nitrogen atom (the same carbon atom to which three nitrogen atoms are bonded together). Here, "two or more kinds 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 21 to} R ²⁴ , only three or all (four) are hydrocarbon groups, and any two or three hydrocarbon groups are bonded in this way. There are cases where only are bonded to each other, and cases where ^{all (4 types) of R 21 to} R ²⁴ are hydrocarbon groups, and all of these hydrocarbon groups are bonded to each other. The method is the same as in the case of ^{R 11 to} R ^13.

In the 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 which is present and the carbon atom bonded to the nitrogen atom or the nitrogen atom bonded to the carbon atom. Here, "two or more kinds 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, when ^{only two or all (three) of R 31 to} R ³³ are hydrocarbon groups and only one of the two hydrocarbon groups are bonded to each other in this way. And, ^{all (3 types) of R 31 to} R ³³ are hydrocarbon groups, and all of these hydrocarbon groups may be bonded to each other, and the method of bonding the hydrocarbon groups to each other is also R ^{11 to R.} It is the same as the case of ^13.

^{When two or more of R 41} , R ⁴² , R ⁴³ and R ^{44 in} the general formula (1) -14 are hydrocarbon groups, these hydrocarbon groups are bonded to each other and these hydrocarbon groups are formed. A ring may be formed together with the bonded nitrogen atom and the carbon atom bonded to the nitrogen atom (the same carbon atom to which three nitrogen atoms are bonded together). Here, "two or more kinds 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 are bonded in this way. There are cases where only are bonded to each other, and cases where ^{all (4 types) of R 41 to} R ⁴⁴ are hydrocarbon groups, and all of these hydrocarbon groups are bonded to each other. The method is the same as in the case of ^{R 11 to} R ^13.

Compound (1) is represented by the following general formula (1) -1 (hereinafter, may be abbreviated as "compound (1) -1") and the following general formula (1) -2. A compound (hereinafter, may be abbreviated as "Compound (1) -2") and a compound represented by the following general formula (1) -3 (hereinafter, may be abbreviated as "Compound (1) -3"). ), And compounds represented by the following general formula (1) -4 (hereinafter, may be abbreviated as "Compound (1) -4").

General formula (1) -1 to General formula (1) -4, 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 the same as described above. )

Preferred compounds (1) -1 are, for example, a compound represented by the following general formula (1) -1A (hereinafter, may be abbreviated as "Compound (1) -1A"), and the following general formula. (1) Examples thereof include a compound represented by -1B (hereinafter, may be abbreviated as "Compound (1) -1B").

Formula (1) -1A and the general formula (1) in -1B, G is as defined ^{above; R 11 ', R 12'} and ^{R 13} 'are each independently a hydrogen atom or a hydrocarbon group; R ⁰¹¹ is a hydrocarbon ring.

Formula (1) -1A and the general formula (1) in ^{-1B, R 11 ', R 12} ' and ^{R 13} 'are each independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon group for ^{R 11 ',} R ^12' and ^{R 13} ', except that there is no possible to form a ring with each other is the same as the hydrocarbon group for ^R 11 ^{to R 13} above .. That is, the compound (1) -1A ^{is, R 11 ', R 12'} also and ^{R 13} 'is in any of the group, the general formula (1) -1A imidazole skeleton described in are condensed structure Does not have.
^{R 11 ',} R ^12' and ^{R 13} 'is a hydrogen atom, is preferably an alkyl group or an aryl group.

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

As preferred compounds (1) -1A, for ^{example, R 11 ', R 12',} at least one and ^{R 13} 'can be mentioned those in which hydrogen atom.
Preferred compounds (1) -1B include, for example, those in which R ⁰¹¹ is an aromatic hydrocarbon ring.

Preferred compounds (1) -2 include, for example, a compound represented by the following general formula (1) -2A (hereinafter, may be abbreviated as "Compound (1) -2A") and the following general formula ( 1) A compound represented by -2B (hereinafter, may be abbreviated as "Compound (1) -2B"), a compound represented by the following general formula (1) -2C (hereinafter, "Compound (1)-". (Sometimes abbreviated as "2C"), the compound represented by the following general formula (1) -2D (hereinafter, sometimes abbreviated as "Compound (1) -2D"), and the following general formula (1)- Examples thereof include a compound represented by 2E (hereinafter, may be abbreviated as “Compound (1) -2E”).

In the general formula (1) -2A~ formula (1) -2E, G is as defined ^{above; R 21 ', R 22'} , R 23 ' and ^{R 24'} each independently represent a hydrogen atom or a hydrocarbon It is a group; R ⁰²¹ , R ⁰²² and R ⁰²³ are independently nitrogen-containing rings.

In the general formula (1) -2A~ formula ^{(1) -2E, R 21 '} , R 22', R 23 ' and ^{R 24'} are each independently a hydrogen atom or a hydrocarbon group.
^{R 21 ',} R ^22', wherein the hydrocarbon group in ^{R 23} 'and ^{R 24',} except that there is no possible to form a ring with each other, the hydrocarbon group in ^R 11 ^{to R 13} above Is the same as.
^{R 21 ', R 22',} R 23 ' and ^{R 24'} is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably an alkyl group or an aryl group.

In the general formula (1) -2B, R ⁰²¹ is a nitrogen-containing ring. In addition, in this specification, a "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 this general formula, and 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. ^R021 may be either monocyclic or polycyclic, and is usually an aliphatic nitrogen-containing ring.
Compound (1) -2B is a compound (1) -2 in which the hydrocarbon groups R ²¹ and R ²² are bonded to each other to form a ring.

In the general formula (1) ^{-2C, R 022} is a nitrogen-containing cyclic. That is, in the general formula (1) ^{-2C, R 022,} this generally of three nitrogen atoms that are listed in the ^formula, one nitrogen atom of ^{which R 21} 'and ^{R 24'} are not joined together Is a ring structure (nitrogen-containing cyclic group) having a ring skeleton as a constituent atom. R ⁰²² may be either 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 hydrocarbon groups R ²² and R ²³ are bonded to each other to form a ring.

In the general formula (1) -2D, R ⁰²³ is a nitrogen-containing ring. That is, in the general formula (1) -2D, R ^023, of the three nitrogen atoms that are listed in this general formula, the two nitrogen atoms to which R ^{21 'is} not bound, these two It is a ring structure (nitrogen-containing cyclic group) in which one carbon atom located between the nitrogen atoms of the above is a constituent atom of the ring skeleton. R ⁰²³ may be either 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 hydrocarbon groups R ²³ and R ²⁴ are bonded to each other to form a ring.

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

Compound (1) as preferred in -2A, for ^{example, R 21 ', R 22'} , are those ^{R 23} 'and ^{R 24'} are all alkyl group or an aryl group.
Preferred compounds (1) -2C include, for example, those in which R ⁰²² is an aliphatic nitrogen-containing ring.
Preferred compounds (1) -2D include, for example, those in which R ⁰²³ is an aliphatic nitrogen-containing ring.
Preferred compounds (1) -2E include, for example, those in which R ⁰²³ has an aliphatic nitrogen-containing ring ( ^{both R 021} and R ⁰²³ have an aliphatic nitrogen-containing ring).

Preferred compounds (1) -3 are, for example, compounds represented by the following general formula (1) -3A (hereinafter, may be abbreviated as "Compound (1) -3A"), the following general formula ( 1) A compound represented by -3B (hereinafter, may be abbreviated as "Compound (1) -3B"), a compound represented by the following general formula (1) -3C (hereinafter, "Compound (1)-". 3C ”) and compounds represented by the following general formulas (1) -3D (hereinafter, may be abbreviated as“ Compound (1) -3D ”).

Formula (1) -3A～ formula (1) in -3D, G is as defined ^{above; R 31 ', R 32'} and ^{R 33} 'are each independently a hydrogen atom or a hydrocarbon group; R ⁰³¹ and R ⁰³² and R ⁰³³ are independently nitrogen-containing rings.

Formula (1) -3A～ formula (1) in ^{-3D, R 31 ', R 32} ' and ^{R 33} 'are each independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon group for ^{R 31 ',} R ^32' and ^{R 33} ', except that there is no possible to form a ring with each other is the same as the hydrocarbon group for ^R 11 ^{to R 13} above ..
R ³¹ ', R ³² ' and R ^{33'preferably} are hydrogen atoms, alkyl groups or aryl groups.

In the general formula (1) -3B, ^R031 is a nitrogen-containing ring. That is, in the general formula (1) -3B, R ^{031 is one nitrogen atom to which R 31'is} not bonded and two of the two nitrogen atoms described in this general formula. It is a ring structure (nitrogen-containing cyclic group) in which one carbon atom located between the nitrogen atoms of the above is a constituent atom of the ring skeleton. R ⁰³¹ may be either 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 hydrocarbon groups R ³² and R ³³ are bonded to each other to form a ring.

In the general formula (1) -3C, ^R032 is a nitrogen-containing ring. That is, in the general formula (1) -3C, R ⁰³² rings the two nitrogen atoms described in the general formula and one carbon atom located between these two nitrogen atoms. It is a ring structure (nitrogen-containing cyclic group) that is a constituent atom of the skeleton. R ⁰³² may be either 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 hydrocarbon groups R ³¹ and R ³³ are bonded to each other to form a ring.

In the general formula (1) -3D, R ⁰³³ is a nitrogen-containing ring. That is, in the general formula (1) -3D, R ^033, of the two nitrogen atoms that are listed in this general formula, and one of the nitrogen atoms of R ^{33 'is} not bound, these two It is a ring structure (nitrogen-containing cyclic group) in which one carbon atom located between the nitrogen atoms of the above is a constituent atom of the ring skeleton. R ⁰³³ may be either monocyclic or polycyclic, and is usually an aliphatic nitrogen-containing ring.
Compound (1) -3D is a compound (1) -3 in which hydrocarbon groups R ³¹ and R ³² are bonded to each other to form a ring.

Preferred compounds (1) -3A include, for example, those in which at least one of ^{R 31} ', R ³² ' and R ^{33'is a hydrogen atom.}
Preferred compounds (1) -3B include, for example, those in which ^R031 is an aliphatic nitrogen-containing ring.
Preferred compounds (1) -3C include, for example, those in which ^R032 is an aliphatic nitrogen-containing ring.

Preferred compounds (1) -4 are, for example, compounds represented by the following general formula (1) -4A (hereinafter, may be abbreviated as "Compound (1) -4A"), the following general formula ( 1) A compound represented by -4B (hereinafter, may be abbreviated as "Compound (1) -4B"), a compound represented by the following general formula (1) -4C (hereinafter, "Compound (1)-" (Sometimes abbreviated as "4C"), the compound represented by the following general formula (1) -4D (hereinafter, sometimes abbreviated as "Compound (1) -4D"), and the following general formula (1)- Examples thereof include a compound represented by 4E (hereinafter, may be abbreviated as “Compound (1) -4E”).

Formula (1) -4A～ formula (1) in-4E, G is as defined ^{above; R 41 ', R 42'} , R 43 ' and ^{R 44'} each independently represent a hydrogen atom or a hydrocarbon It is a group; R ⁰⁴¹ , R ⁰⁴² and R ⁰⁴³ are independently nitrogen-containing rings.

Formula (1) -4A～ formula (1) in ^{-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 bond to each other to form a ring. Is the same as.
Formula (1) -4A~ (1) in ^{-4E, R 41 ', R 42} ', R 43 ' and ^{R 44'} is preferably a hydrogen atom, an alkyl group or an aryl group, an alkyl group or an aryl More preferably it is a group.

In the general formula (1) -4B, R ⁰⁴¹ is a nitrogen-containing ring. That is, in the general formula (1) -4B, R ^041, of the three nitrogen atoms that are listed in this general formula, the nitrogen atom attached to the carbon atom of the carbonyl group, R ^{43 'and} and the nitrogen atom to which R ^{44 'are} joined together, a nitrogen atom that does not correspond to any of a ring structure as a constituent atom of the ring skeleton (nitrogen-containing cyclic group). R ⁰⁴¹ may be either 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 hydrocarbon groups R ⁴¹ and R ⁴² are bonded to each other to form a ring.

In the general formula (1) -4C, ^R042 is a nitrogen-containing ring. That is, in the general formula (1) -4C, R ⁰⁴² refers to 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 ring-type group) in which an atom and one carbon atom located between these two nitrogen atoms are constituent atoms 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 hydrocarbon groups R ⁴² and R ⁴³ are bonded to each other to form a ring.

In the general formula (1) -4D, R ⁰⁴³ is a nitrogen-containing ring. That is, in the general formula (1) -4D, R ^043, of the three nitrogen atoms that are listed in this general formula, the nitrogen atom attached to the carbon atom of the carbonyl group, R ^{41 'and} and the nitrogen atom to which R ^{42 'are} joined together, a nitrogen atom that does not correspond to any of a ring structure as a constituent atom of the ring skeleton (nitrogen-containing cyclic group). R ⁰⁴³ may be either 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 hydrocarbon groups R ⁴³ and R ⁴⁴ are bonded to each other to form a ring.

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

Compound (1) as preferred in -4A, for ^{example, R 41 ', R 42'} , are those ^{R 43} 'and ^{R 44'} are all alkyl group or an aryl group.
Preferred compounds (1) -4B include, for example, those in which R ⁰⁴¹ is an aliphatic nitrogen-containing ring.
Preferred compounds (1) -4D include, for example, those in which R ⁰⁴³ is an aliphatic nitrogen-containing ring.
Preferred compounds (1) -4E include, for example, those in which R ⁰⁴¹ and R ⁰⁴³ are aliphatic nitrogen-containing rings.

Among the compounds (1), more preferable ones include compound (1) -1A, compound (1) -2E, compound (1) -3A and compound (1) -4A.
Among the compounds (1), particularly preferable ones include compound (1) -1A-1 and compound (1) -1A-2.

In the Formula (1) -1A-1 and the general formula ^{(1) -1A-2, R} 1, R 2, R 11 ', R 12' and ^{R 13 'are} the same as above.

<Production method of compound (1)>
Compound (1) can be produced, for example, by using a technique for forming an ester structure or an amide structure.
Examples of the method for producing the compound represented by the general formula (1) -A and the compound represented by the general formula (1) -B, which are preferable examples of the compound (1), are represented by the following general formula (1a). (Hereinafter, it may be abbreviated as "Compound (1a)") or a compound represented by the following general formula (1b) (hereinafter, may be abbreviated as "Compound (1b)") and the following. The compound represented by the general formula (1c) (hereinafter, may be abbreviated as "compound (1c)") is reacted with each other to form the compound represented by the general formula (1) -A or the general formula (1). )-A production method having a step of obtaining the compound represented by B can be mentioned.

Formula (1a) ~ ^R 1 to R ³ in the general formula (1c) is represented by the general formula (1) -A and the general formula (1) is the same as ^R 1 to R ³ in -B, the formula ( X in 1c) is the same as X in the general formula (1).

The reaction between compound (1a) or compound (1b) and compound (1c) is preferably carried out using a solvent.
The solvent is not particularly limited and may be appropriately selected depending on the type of the compound (1a) to the compound (1c). Preferred solvents include, for example, ethers such as tetrahydrofuran (THF); ketones such as acetone and methyl ethyl ketone (MEK); dichloromethane (DCM) and the like.
The solvent may be used, for example, by mixing with any component other than the solvent such as compound (1a) to compound (1c) and dissolving or dispersing this component in advance, or the solvent as described above. A solvent may be used by mixing with these components without dissolving or dispersing any of the components other than the above in advance.

As the solvent, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

The amount of the solvent used during the reaction is not particularly limited, but is preferably 1 to 100 times by mass with respect to the total amount of the compound (1a) or the compound (1b) and the compound (1c) used. More preferably, it is 2 to 60 times by mass.

The temperature and reaction time at the time of reaction between compound (1a) or compound (1b) and compound (1c) may be appropriately adjusted.
The reaction between the compound (1a) or the compound (1b) and the compound (1c) is preferably carried out by reducing the water content of the reaction system. For example, the reaction may be carried out using a dry solvent, nitrogen gas or argon gas. , It is preferable to carry out the reaction in an atmosphere of an inert gas such as helium gas.

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

The compound represented by the general formula (1) -A, which is a preferable example of the compound (1), is, for example, abbreviated as the compound represented by the following general formula (1d) (hereinafter, abbreviated as "compound (1d)"). May be produced by reacting with a compound represented by the following general formula (1e) (hereinafter, may be abbreviated as “compound (1e)”).

In the general formula (1d) and the general formula (1e), R ¹ and X are the same as described above; L is a halogen atom. L is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.
The preferable conditions for the reaction between the compound (1d) and the compound (1e) are the same as the preferable conditions for the reaction between the compound (1a) or the compound (1b) and the compound (1c).

<Base conversion growth agent>
The base conversion breeding agent of the present disclosure contains a compound represented by the following general formula (1), and by the action of the base and the epoxy compound having an epoxy group, a new base is generated and the newly generated base is generated. A new base is also generated by the action of the base and the epoxy compound.

In the general formula (1), G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or , A group containing a hydrocarbon group which does not have a hydrogen atom bonded to the β-position or does not have a β-position with respect to the ester structure and may have a substituent, or an adjacent carbonyl group and an amide structure. The nitrogen atom to be formed is bonded to the nitrogen atom, and the pKa of the β-position hydrogen atom with respect to the amide structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position. Is a group containing a hydrocarbon group which may have a substituent in the absence of, and X is the following general formula (1) -11, (1) -12, (1) -13 or (1). It is a group represented by -14.

General formula (1) -11 to General formula (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 independent hydrogen atoms or hydrocarbon groups, respectively, and when ^{two or more of R 11} , R ¹² and R ¹³ are hydrocarbon groups, these hydrocarbon groups are mutually exclusive. It may be bonded to to form a ring, and 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 to form a ring. It may be formed, and when ^{two or more of R 31} , R ³² and R ³³ are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring, and R ^41. , R ⁴² , R ⁴³ and R ⁴⁴ , where two or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; It is formed for the carbon atom to which X is bonded.

Compound (1) functions as a base conversion breeding agent regardless of the number of epoxy groups contained in one molecule of the epoxy compound. However, in order for the curable composition described later to be curable, an epoxy compound having two or more epoxy groups in one molecule is required in this curable composition.

It is presumed that the base conversion breeding agent acts as follows.
That is, a base generator that generates a base by light irradiation or heating (in this specification, it may be simply referred to as a "base generator") is represented by the following general formula (9) -1 by light irradiation or heating. When a base (hereinafter referred to as "base (9) -1") is generated, the base (9) -1 is an epoxy compound represented by the following general formula (9) -2 (hereinafter, "epoxy"). It acts on compound (9) -2 ") to produce a compound represented by the following general formula (9) -3. The compounds are furthermore the action of a base (9) -1, a hydroxyl group (-OH) is an anion (-O ^-), and the anionic compound (hereinafter, referred to as "anionic compound (9) -3 ') becomes .. This anionic compound (9) -3 acts on the compound (1) which is a base conversion and multiplying agent, decomposes the compound (1) to generate a new compound (1e) as a base, and has the following general formula. (9) A compound represented by -4 (hereinafter referred to as "Compound (9) -4") is produced. The generated base (compound (1e)) further acts on the epoxy compound (9) -2 to form an anion-type compound represented by the following general formula (9) -5 (hereinafter, "anion-type compound (9)-". 5 ”) is generated. A part of the anion type compound (9) -5 further acts on the epoxy compound (9) -2 to finally become a cured product, and a part of the anion type compound (9) -5 newly acts on the compound (1). A new base is generated from the base conversion growth agent.
As described above, the base conversion and multiplying agent of the present disclosure has a base conversion action of separately generating a base by the action of a base and also has a base growth action of self-proliferating to generate a base.
In the following formula, R ⁹¹ , R ⁹² and R ⁹³ are independently organic groups.

On the other hand, the above-mentioned "JF Cameron, JM J. Frechet, J. Am. Chem. Soc. 1991, 113, 4303." (Non-Patent Document 1), "M. Shirai, M. Tsunooka, Prog. Polymer. Sci. 1996, 21, 1. "(Non-Patent Document 2)," K. Arimitsu, R. Endo, Chem. Meter. 2013, 25, 4461-4463. "(Non-Patent Document 3). The conventional photobase generator disclosed in the above literature generates not only base but also carbon dioxide (CO ₂ ) due to decomposition by exposure.
On the other hand, the base conversion breeding agent of the present disclosure generates a base when decomposed by the action of an anionic compound as described above, but does not generate carbon dioxide, but due to the generation of the base. Residues are incorporated into the cured product. That is, the base conversion breeding agent of the present disclosure has an advantage that it does not generate carbon dioxide or other unnecessary decomposition products in exhibiting its action.

<Curable composition>
The curable composition of the present disclosure contains an epoxy compound having two or more epoxy groups in one molecule, and a compound represented by the above general formula (1). Further, the curable composition of the present disclosure preferably further contains a base generator that generates a base by irradiation with light or heating.

[Epoxy compound]
The curable composition of the present disclosure contains an epoxy compound having two or more epoxy groups in one molecule. The epoxy compound is not particularly limited and can be arbitrarily selected depending on the intended purpose.
The epoxy compound may be, for example, any of a monomer, an oligomer and a polymer, and may be any of a small molecule compound and a polymer compound.

The epoxy compound contained in the curable composition may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily set.

[Compound represented by the general formula (1)]
The curable composition of the present disclosure contains the compound represented by the above-mentioned general formula (1). The compound represented by the general formula (1) contained in the curable composition may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily set.

Further, the compound represented by the general formula (1) preferably contains at least one of the compound represented by the above-mentioned general formula (1) -A and the compound represented by the general formula (1) -B. It is more preferable to include the compound represented by the above-mentioned general formula (1) -A.
Since the curable composition contains the compound represented by the above-mentioned general formula (1) -A, the curable composition containing the compound and the epoxy compound is excellent in thermal stability. Therefore, when a base generator that generates a base by light irradiation is further used in combination, it is possible to suppress the reaction of the curable composition when it is not irradiated with light, and the curable composition has excellent storage stability and storage stability. Both curability can be achieved. Further, since the reaction of the curable composition is suppressed even when the non-irradiated region of the curable composition is heated, the curing of the non-light-irradiated region is suppressed and the light irradiation is performed. It is possible to cure the formed region and it is excellent in pattern forming property.

In the curable composition, the content of the compound represented by the general formula (1) is preferably 3% by mass to 15% by mass, preferably 4% by mass to 12% by mass, based on the content of the epoxy compound. Is more preferable, and 5% by mass to 10% by mass is further preferable. When the content of the compound represented by the general formula (1) is 3% by mass or more, the base proliferation action can be obtained more remarkably when used in combination with a base generator described later. Further, when the content of the compound represented by the general formula (1) is 15% by mass or less, excessive use of this compound is suppressed.

[Base generator]
The curable composition of the present disclosure preferably further contains a base generator that generates a base by irradiation with light or heating. As a result, the compound represented by the general formula (1) newly generates a base and is newly generated by the action of the base generated from the base generator by light irradiation or heating and the epoxy compound. A new base is also generated by the action of the base and the epoxy compound. That is, in the curable composition of the present disclosure, the compound represented by the general formula (1) has a base conversion action of separately generating a base by the action of a base generated from a base generator, and also has a self-propagating base. Has a base proliferating action to generate.
Therefore, in the curable composition of the present disclosure, even when the composition layer is formed thick, poor curing is suppressed and the curability is excellent. This is because if the surface of the composition layer and the shallow region in the vicinity thereof are irradiated with light or heated, bases are generated in a chain reaction to the deep part not irradiated with light or heated due to the base proliferation action. This is because it is easy to cure in a deep part even if it is formed thick.

The base generator is not particularly limited as long as it generates a base by light irradiation or heating, and may be a known compound.

Examples of the base generator that generates a base by light irradiation include those that generate a base by irradiation (exposure) of light having a wavelength of 1 nm to 400 nm.
For example, a nonionic photobase generator that generates a primary amine or a secondary amine by exposure, and a guanidine type strong base by exposure, which are disclosed in the above-mentioned Non-Patent Documents 1 to 3 and the like. Examples thereof include a nonionic photobase generator to be generated.

Examples of the base generator that generates a base by heating include those that generate a base by heating at 60 ° C. to 160 ° C.
Examples of the base generator that generates a base by heating include compounds before the reaction in the following chemical formulas.

The base generator contained in the curable composition may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily set.

In the curable composition, the content of the base generator is preferably 3% by mass to 35% by mass, more preferably 5% by mass to 30% by mass, based on the content of the epoxy compound. It is more preferably 10% by mass to 25% by mass. When the content of the base generator is 3% by mass or more, the curing of the curable composition proceeds more easily. Further, when the content of the base generator is 35% by mass or less, the excessive use of the base generator is suppressed.

[Other ingredients]
The curable composition of the present disclosure may further contain other components in addition to the epoxy compound, the compound represented by the general formula (1), and the base generator.
The other components are not particularly limited as long as the effects of the present invention are not impaired, and can be arbitrarily selected depending on the intended purpose.
The other components contained in the curable composition may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily set.
Examples of other components include epoxy compounds having only one epoxy group in one molecule, sensitizers, fillers, pigments, solvents and the like. In the present disclosure, the term "epoxy compound" simply means "an epoxy compound having two or more epoxy groups in one molecule" described above, unless otherwise specified.

(Epoxy compound having only one epoxy group in one molecule)
The curable composition may contain an epoxy compound having only one epoxy group in one molecule. Thereby, the properties such as the viscosity of the curable composition can be adjusted.
The epoxy compound having only one epoxy group in one molecule may be, for example, any of a monomer, an oligomer and a polymer, and may be any of a low molecular weight compound and a high molecular weight compound.
The epoxy compound contained in the curable composition and having only one epoxy group in one molecule may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be set to.
The content of the epoxy compound having only one epoxy group in one molecule of the curable composition is not particularly limited, and depends on, for example, the content of the epoxy compound having two or more epoxy groups in one molecule. It may be adjusted as appropriate.

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

(Filler)
The curable composition may contain a filler. Thereby, the properties such as the viscosity of the curable composition and the strength of the cured product can be adjusted.
The filler may be a known one and is not particularly limited. For example, the filler may be fibrous, plate-like or granular, and the shape, size and material thereof may be appropriately selected depending on the intended purpose.
The filler contained in the curable composition may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily set.
The content of the filler in the curable composition is not particularly limited and may be appropriately adjusted according to the intended purpose.

(Pigment)
The curable composition may contain a pigment. Thereby, the light transmittance and the like of the cured product can be adjusted.
The pigment contained in the curable composition may be a known pigment, and may be any pigment such as white, blue, red, yellow, and green, and is not particularly limited.
The pigment contained in the curable composition may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily set.
The content of the pigment in the curable composition is not particularly limited and may be appropriately adjusted according to the intended purpose.

(solvent)
The curable composition may contain a solvent. This can improve the handleability of the curable composition.
The solvent is not particularly limited, and may be appropriately selected in consideration of the solubility, stability, etc. of the epoxy compound, the compound represented by the general formula (1), and the base generator.
Specific examples of the solvent include halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene, o-xylene, m-xylene and p-xylene; and aliphatic hydrocarbons such as hexane, heptane and octane. Carous acid esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF) and 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methylethylketone (MEK), cyclohexanone and cyclopentanone; Nitriles such as acetonitrile; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide and the like can be mentioned.
The solvent contained in the curable composition may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily set.

The content of the solvent in the curable composition is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 75% by mass, and 40% by mass with respect to the total amount of the curable composition. It is more preferably ~ 70% by mass. When the content of the solvent is in such a range, the handleability of the curable composition can be further improved.

The curable composition can be obtained by blending an epoxy compound, a compound represented by the general formula (1), a base generator, and if necessary, other components. After blending each component, the obtained one may be used as it is as a curable composition, or the one obtained by continuously performing a known purification operation or the like may be used as a curable composition if necessary.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all components may be added sequentially and mixed. good.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of rotating and mixing 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 compounding is not particularly limited as long as each compounding component is not deteriorated, and can be, for example, 3 ° C. to 30 ° C.
The blending time is also not particularly limited as long as each blending component is not deteriorated, and can be, for example, 0.5 hour to 1 hour.
However, these compounding conditions are only an example.

<Cured product>
The cured product of the present disclosure is obtained by reacting the curable composition of the present disclosure. More specifically, a cured product can be obtained by irradiating the curable composition of the present disclosure with light or heating the curable composition of the present disclosure. Moreover, you may combine light irradiation and heating as needed.
When a cured product is produced by irradiating with light, the curable composition preferably contains a base generator that generates a base by irradiating with light. On the other hand, when a cured product is produced by heating, the curable composition preferably contains a base generator that generates a base by heating.
The shape of the cured product can be arbitrarily selected depending on the purpose, for example, a film shape or a linear shape.

The curable composition may be adhered to a target product by a known method, prebaked (dried) as necessary, and then cured by light irradiation or heating.
For example, when producing a film-like cured product (cured film), an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, etc. The purpose is to apply the curable composition to the target product by using various coaters such as Meyer bar coater and kiss coater, or a coating means such as an applicator, or to immerse the target product in the curable composition. The curable composition may be attached to the object.
For example, in the case of producing a film-like or linear cured product (cured film), a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method, a dispenser printing method, a jet dispenser printing method, and a gravure The curable composition may be attached to the target product by using a printing means such as a printing method, a gravure offset printing method, or a pad printing method.
Prebaking can be performed under the conditions of, for example, 50 ° C. to 80 ° C., 1 minute to 10 minutes, but the conditions are not limited to this.

When the curable composition is irradiated with light to produce a cured product, the wavelength of the light at the time of light irradiation of the curable composition is preferably, for example, 200 nm to 500 nm.
Also, illuminance of the light at the time of light irradiation, for ^example, is preferably ^{30mW / cm 2 ~100mW / cm 2} , irradiation amount, for ^example, is preferably ^{800mJ / cm 2 ~8000mJ / cm 2} .

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

When the curable composition is heated to produce a cured product, the heating temperature of the curable composition is preferably, for example, 80 ° C. to 160 ° C.
The heating time during heating is preferably, for example, 0.5 hours to 2 hours.

The thickness of the cured product may be appropriately set according to the purpose and is not particularly limited. As described above, the curable composition of the present disclosure has an excellent effect that even if the composition layer is thick, the curability is high in a deep part away from the surface of the composition layer, so that the thickness of the cured product is high. It is also possible to increase. The thickness of the cured product may be, for example, 1 μm to 500 μm, 5 μm to 200 μm, or 10 μm to 100 μm. In order to form a cured product having such a thickness, the thickness of the composition layer may be in the same range.

The cured product can have, for example, a pencil hardness of 5B or more, and is, for example, a cured product having a pencil hardness of any one of 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H and the like. Can be obtained. Here, the "pencil hardness" means a value measured in accordance with JIS K5600-5-4: 1999.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Production of compound (1) -A-101>
[Example 1]
As shown below, 1-butanol was reacted with carbonyldiimidazole to produce compound (1) -A-101.
That is, carbonyldiimidazole (3.4 g) was dissolved in dry tetrahydrofuran (THF) (10 mL). Separately, 1-butanol (1.48 g) was mixed with dry tetrahydrofuran (THF) (10 mL) and potassium hydroxide (3 drops).
Next, while heating the THF solution of carbonyldiimidazole obtained above, the THF solution of 1-butanol obtained above was added dropwise thereto, and after completion of the addition, the obtained mixed solution was added to the mixture at 60 ° C. 4 The reaction was carried out by stirring for 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 phase was removed to wash the reaction solution. Further, the reaction solution was washed twice with the same saturated aqueous sodium chloride solution, and then the organic layer was concentrated to obtain the target compound (1) -A-101 as a colorless liquid (yield). 2.1 g, yield 63%)
Table 1 shows the analysis results of the obtained compound (1) -A-101 by ^{1 1 H-NMR.}

The thermal decomposition temperature of compound (1) -A-101 was measured under the following conditions and found to be 165 ° C. The intersection of the tangents of the DTA curve before and after the temperature at which the mass change of the measurement sample was observed was defined as the thermal decomposition temperature.
Equipment: TG-DTA (TG-DTA2000s and MTC1000s, manufactured by MacScience Co., Ltd.)
Atmosphere: Nitrogen atmosphere Temperature rise rate: 10 ° C / min

<Production of compound (1) -B-101>
[Example 2]
As shown below, 1-aminobutane was reacted with carbonyldiimidazole to produce compound (1) -B-101.
That is, carbonyldiimidazole (3.6 g) was dissolved in dry tetrahydrofuran (THF) (10 mL). Separately, 1-aminobutane (1.4 g) was mixed with dry tetrahydrofuran (THF) (10 mL).
Next, the THF solution of 1-aminobutane obtained above was added dropwise to the THF solution of carbonyldiimidazole obtained above, and after completion of the addition, the obtained mixed solution was stirred at room temperature for 0.5 hours. , Reacted.
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 phase was removed to wash the reaction solution. Further, the reaction solution was washed twice with the same saturated aqueous sodium chloride solution, and then the organic layer was concentrated to obtain the target compound (1) -B-101 as a colorless liquid (yield). 2.5 g, yield 78%)
Table 2 shows the analysis results of the obtained compound (1) -B-101 by ^{1 1 H-NMR.}

When the thermal decomposition temperature of compound (1) -B-101 was measured in the same manner as in Example 1, it was 134 ° C.

<Production of compound (1) -A-102>
[Example 3]
As shown below, compound (1) -A-102 was prepared by reacting butoxycarbonyl chloride with 2-ethyl-4-methylimidazole.
That is, 2-ethyl-4-methylimidazole (1.13 g) was dissolved in dry tetrahydrofuran (THF) (20 mL). Separately, butoxycarbonyl chloride (0.7 g) was mixed with dry tetrahydrofuran (THF) (10 mL).
Next, the THF solution of butoxycarbonyl chloride obtained above was added dropwise to the THF solution of 2-ethyl-4-methylimidazole obtained above, and after completion of the addition, the obtained mixed solution was allowed to cool at 0 ° C. for 3 hours. The reaction was carried out by stirring.
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 phase was removed to wash the reaction solution. Further, the reaction solution was washed twice with the same saturated aqueous sodium chloride solution, and then the organic layer was concentrated to obtain the target compound (1) -A-102 as a yellow liquid (yield). 0.82 g, yield 78%)
Table 3 shows the analysis results of the obtained compound (1) -A-102 by ^{1 1 H-NMR.}

<Production of compound (1) -A-103>
[Example 4]
As shown below, compound (1) -A-103 was produced by reacting butoxycarbonyl chloride with 2-methylimidazole.
That is, 2-methylimidazole (0.82 g) was dissolved in dry tetrahydrofuran (THF) (20 mL). Separately, butoxycarbonyl chloride (0.68 g) was mixed with dry tetrahydrofuran (THF) (10 mL).
Next, the THF solution of butoxycarbonyl chloride obtained above was added dropwise to the THF solution of 2-methylimidazole obtained above, and after completion of the addition, the obtained mixed solution was stirred at 0 ° C. for 3 hours. , Reacted.
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 phase was removed to wash the reaction solution. Further, the reaction solution was washed twice with the same saturated aqueous sodium chloride solution, and then the organic layer was concentrated to obtain the target compound (1) -A-103 as a colorless liquid (yield). 0.667g, yield 74%)
Table 4 shows the analysis results of the obtained compound (1) -A-103 by ^{1 1 H-NMR.}

<Production of compound (1) -A-104>
[Example 5]
As shown below, compound (1) -A-104 was prepared by reacting butoxycarbonyl chloride with 1,1,3,3-tetramethylguanidine.
That is, 1,1,3,3-tetramethylguanidine (1.13 g) was dissolved in dry tetrahydrofuran (THF) (20 mL). Separately, butoxycarbonyl chloride (0.7 g) was mixed with dry tetrahydrofuran (THF) (10 mL).
Next, the THF solution of butoxycarbonyl chloride obtained above was added dropwise to the THF solution of 1,1,3,3-tetramethylguanidine obtained above, and after completion of the addition, the obtained mixed solution was added to 0 ° C. The reaction was carried out by stirring with the mixture 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 phase was removed to wash the reaction solution. Further, the reaction solution was washed twice with the same saturated aqueous sodium chloride solution, and then the organic layer was concentrated to obtain the target compound (1) -A-104 as a colorless liquid (yield). 1.118 g, yield 94%)
Table 5 shows the analysis results of the obtained compound (1) -A-104 by ^{1 1 H-NMR.}

<Manufacturing of reference compound (1)>
[Reference example 1]
As shown below, 4-methoxybenzoyl chloride was reacted with imidazole to produce reference compound (1).
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 cooling the THF solution of imidazole obtained above in an ice bath, the THF solution of 4-methoxybenzoyl chloride obtained above was added dropwise thereto, and after completion of the addition, the obtained mixed solution was brought to room temperature. The reaction was carried out by stirring with the mixture 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 phase was removed to wash the reaction solution. Further, the reaction solution was washed with the same saturated aqueous sodium chloride solution four times, and then the organic layer was concentrated to obtain the target reference compound (1) as a pale yellow solid (yield 1. 0 g, yield 50%)
^{Table 6 shows the results of 1} H-NMR analysis of the obtained reference compound (1).

When the thermal decomposition temperature of the reference compound (1) was measured in the same manner as in Example 1, it was 247 ° C.

<Manufacturing of curable composition>
[Example 6]
Contains bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -A-101 (17 mol% with respect to epoxy compound), and chloroform (0.60 g), which are epoxy compounds. Then, the mixture was stirred at 25 ° C. for 1 minute to obtain a curable composition.

(Curing of curable composition)
Using an applicator, the curable composition obtained above was applied onto a silicon substrate. Next, the coating film (composition layer) was heated (prebaked) at 60 ° C. for 3 minutes and then heated at 140 ° C. for 60 minutes. The FT-IR spectrum was measured by FT-IR (Fourier transform infrared spectroscopy) using the heated coating film. The results are shown in FIG.
As shown in FIG. 1, it was confirmed that the peak was reduced due to the epoxy group near ^{910 cm -1 by heating.} Further, FIG. 2 shows a change in the peak area ratio due to the epoxy group due to heating.
As shown in FIG. 2, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is about 0.6, and about 40% of the epoxy groups react with each other by heating to form a cured product. It is presumed that there is.

<Manufacturing of curable composition>
[Example 7]
Contains bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -B-101 (17 mol% with respect to epoxy compound), and chloroform (0.60 g), which are epoxy compounds. Then, the mixture was stirred at 25 ° C. for 1 minute to obtain a curable composition.
A coating film (composition layer) was formed and heated in the same manner as in Example 6. The FT-IR spectrum was measured using the heated coating film.
As shown in FIG. 2, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is almost 0, and about 99% or more of the epoxy groups react with each other by heating to form a cured product. It is speculated.
From the above, it is presumed that the curable composition of Example 6 is superior in thermal stability to the curable composition of Example 7.

<Manufacturing of curable composition>
[Reference example 2]
25 Stirring at ° C. for 1 minute gave a curable composition.
A coating film (composition layer) was formed and heated in the same manner as in Example 6. The FT-IR spectrum was measured using the heated coating film.
As shown in FIG. 2, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is almost 0, and about 99% or more of the epoxy groups react with each other by heating to form a cured product. It is speculated.
From the above, it is presumed that the curable composition of Example 6 is superior in thermal stability to the curable composition of Reference Example 2.

<Manufacturing of curable composition>
[Reference example 3]
A bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), imidazole (17 mol% with respect to the epoxy compound) and chloroform (0.60 g), which are epoxy compounds, are blended and stirred at 25 ° C. for 1 minute. As a result, a curable composition was obtained.
A coating film (composition layer) was formed and heated in the same manner as in Example 6. The FT-IR spectrum was measured using the heated coating film.
As shown in FIG. 2, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is almost 0, and about 99% or more of the epoxy groups react with each other by heating to form a cured product. It is speculated.
From the above, it is presumed that the curable composition of Example 6 is superior in thermal stability to the curable composition of Reference Example 3.

<Manufacturing of curable composition>
[Example 8]
Bisphenol A type epoxy resin which is an epoxy compound (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -A-101 (0.01 g, 5% by mass based on the epoxy compound) and chloroform (0). .60 g) was blended and stirred at 25 ° C. for 1 minute to obtain a curable composition.

(Curing of curable composition)
Using an applicator, the curable composition obtained above was applied onto a silicon substrate. Next, after heating (prebaking) the coating film (composition layer) at 60 ° C. for 3 minutes, an ultraviolet ray having a wavelength of 365 nm is applied to the coating film ^{using an LED lamp under the conditions of an illuminance of 50 mW / cm 2} and an exposure amount of 5000 mJ / cm ^2. Was irradiated.
Next, the coating film after light irradiation was heated at 140 ° C. for 60 minutes to obtain a cured product having a thickness of 15 μm. The FT-IR spectrum was measured by FT-IR (Fourier transform infrared spectroscopy) using the cured product after heating.
From the measurement results of the FT-IR spectrum, the change in the peak area ratio due to the epoxy group due to heating was determined. The results are shown in FIG.
As shown in FIG. 4, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is about 0.6, and about 40% of the epoxy groups react with each other by heating to form a cured product. It is presumed that there is.

<Manufacturing of curable composition>
[Reference example 4]
Bisphenol A type epoxy resin which is an epoxy compound (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), base generator represented by the following formula (8) -101 (0.01 g, 5 mass with respect to the mass of the epoxy compound) %) And chloroform (0.60 g) were blended and stirred at 25 ° C. for 1 minute to obtain a curable composition.

(Curing of curable composition)
A coating film (composition layer) was formed in the same manner as in Example 8, and the coating film was heated after irradiating the coating film with ultraviolet rays. The FT-IR spectrum was measured using the heated coating film.
From the measurement results of the FT-IR spectrum, the change in the peak area ratio due to the epoxy group due to heating was determined. The results are shown in FIG.
As shown in FIG. 4, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is about 0.81, and about 19% of the epoxy groups react with each other by heating to form a cured product. It is presumed that there is.

<Manufacturing of curable composition>
[Example 9]
Bisphenol A type epoxy resin which is an epoxy compound (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -A-101 (0.01 g, 5% by mass based on the epoxy compound), the above-mentioned formula. (8) The base generator represented by −101 (0.01 g, 5% by mass based on the mass of the epoxy compound) and chloroform (0.60 g) are blended and cured by stirring at 25 ° C. for 1 minute. A sex composition was obtained.

(Curing of curable composition)
A coating film (composition layer) was formed in the same manner as in Example 8, and the coating film was heated after irradiating the coating film with ultraviolet rays. The FT-IR spectrum was measured using the heated coating film. The results are shown in FIG.
From the measurement results of the FT-IR spectrum, the change in the peak area ratio due to the epoxy group due to heating was determined. The results are shown in FIG.
As shown in FIG. 3, by heating, reduction in peak due to reduction and 1750 cm ^-1 vicinity of urethane bonds peaks due to the epoxy group in the vicinity of 910 cm ^-1, as well as due to the carbonate structure near 1800 cm ^-1 An increase in the peak was confirmed. That is, it is presumed that the curing reaction of the epoxy compound proceeds by heating, and the compound (1) -A-101 having a urethane bond is decomposed to generate a new base and a carbonic acid ester structure is formed. ..
As shown in FIG. 4, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is about 0.08, and about 92% of the epoxy groups react with each other by heating to form a cured product. It is presumed that there is.
By comparing Example 8 and Reference Example 4 with Example 9, the curable composition in which the base generator represented by the compound (1) -A-101 and the formula (8) -101 was used in combination was determined to be curable. It turns out to be excellent.

<Manufacturing of curable composition>
[Example 10]
Bisphenol A type epoxy resin which is an epoxy compound (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -A-101 (0.01 g, 5% by mass based on the epoxy compound), the above-mentioned formula. (8) The base generator represented by −101 (0.04 g, 20% by mass based on the mass of the epoxy compound) and chloroform (0.60 g) are blended and cured by stirring at 25 ° C. for 1 minute. A sex composition was obtained.

(Curing of curable composition)
Using an applicator, the curable composition obtained above was applied onto a silicon substrate. Next, after heating (prebaking) the coating film (composition layer) at 60 ° C. for 3 minutes, an ultraviolet ray having a wavelength of 365 nm is applied to the coating film ^{using an LED lamp under the conditions of an illuminance of 50 mW / cm 2} and an exposure amount of 5000 mJ / cm ^2. Was irradiated.
Next, the coating film after light irradiation was heated at 140 ° C. for 60 minutes to obtain a cured product having a thickness of 15 μm. The FT-IR spectrum was measured by FT-IR (Fourier transform infrared spectroscopy) using the cured product after heating.
From the measurement results of the FT-IR spectrum, the change in the peak area ratio due to the epoxy group due to heating was determined. The results are shown in FIG.
As shown in FIG. 5, in the coating film after heating for 60 minutes, the peak area ratio with respect to that before heating is about 0.14, and about 86% of the epoxy groups react with each other by heating to form a cured product. It is presumed that there is.

<Manufacturing of curable composition>
[Example 11]
Bisphenol A type epoxy resin which is an epoxy compound (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -A-102 (0.01 g, 5% by mass based on the epoxy compound), the above-mentioned formula. (8) The base generator represented by −101 (0.04 g, 20% by mass based on the mass of the epoxy compound) and chloroform (0.60 g) are blended and cured by stirring at 25 ° C. for 1 minute. A sex composition was obtained.

(Curing of curable composition)
A coating film (composition layer) was formed in the same manner as in Example 10, and the coating film was heated after irradiating the coating film with ultraviolet rays. The FT-IR spectrum was measured using the heated coating film.
From the measurement results of the FT-IR spectrum, the change in the peak area ratio due to the epoxy group due to heating was determined. The results are shown in FIG.
As shown in FIG. 5, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is almost 0%, and about 100% of the epoxy groups react with each other by heating to form a cured product. It is speculated.

<Manufacturing of curable composition>
[Example 12]
Bisphenol A type epoxy resin which is an epoxy compound (Mitsubishi Chemical Co., Ltd., jER828, 0.20 g), the above-mentioned compound (1) -A-103 (0.01 g, 5% by mass based on the epoxy compound), the above-mentioned formula. (8) The base generator represented by −101 (0.04 g, 20% by mass based on the mass of the epoxy compound) and chloroform (0.60 g) are blended and cured by stirring at 25 ° C. for 1 minute. A sex composition was obtained.

(Curing of curable composition)
A coating film (composition layer) was formed in the same manner as in Example 10, and the coating film was heated after irradiating the coating film with ultraviolet rays. The FT-IR spectrum was measured using the heated coating film.
From the measurement results of the FT-IR spectrum, the change in the peak area ratio due to the epoxy group due to heating was determined. The results are shown in FIG.
As shown in FIG. 5, in the coating film after heating for 60 minutes, the peak area ratio to that before heating is about 8%, and about 92% of the epoxy groups react with each other by heating to form a cured product. It is speculated.

The disclosure of Japanese patent application 2018-089281, filed May 7, 2018, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (9)

An epoxy compound having two or more epoxy groups in one molecule,
Compounds represented by the following general formula (1) and
Curable composition containing.

(In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or the ester. Nitrogen that forms an amide structure with a group containing a hydrocarbon group that may have a substituent, that does not have a hydrogen atom bonded to the β-position with respect to the structure or does not have a β-position, or an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, which is bonded to the atom and the nitrogen atom, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. , A group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. It is a group represented.)

(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 independent of each other. When it is a hydrogen atom or a hydrocarbon group and ^{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, 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 2 of R ⁴¹ , R ⁴² , R ⁴³ and R ^44. When the species or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is formed for the carbon atom to which X is bonded. ing.) The curable composition according to claim 1, further comprising a base generator that generates a base by light irradiation or heating. Claim 1 or claim that the compound represented by the general formula (1) includes at least one of the compound represented by the following general formula (1) -A and the compound represented by the general formula (1) -B. 2. The curable composition according to 2.

(In the formula, R ¹ has a pKa of the hydrogen atom at the β-position with respect to the adjacent ester structure of 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent ester structure or the β-position does not exist. It is a hydrocarbon group which may have a substituent, and R ² and R ³ are independently hydrogen atoms or the pKa of the β-position hydrogen atom with respect to the adjacent amide structure is 27 or more, or are adjacent to each other. It is a hydrocarbon group which may have a substituent, in which a hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist, and X is independently the general formula (1) -11, ( 1) A group represented by -12, (1) -13 or (1) -14. At ^{least one of R 2} and R ³ has a pKa of the β-position hydrogen atom with respect to the adjacent amide structure of 27 or more. Alternatively, it is a hydrocarbon group that may have a substituent, with no hydrogen atom attached to the β-position or no β-position with respect to the adjacent amide structure. R ² and R ³ are adjacent amides. The pKa of the hydrogen atom at the β-position with respect to the structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent amide structure or the β-position does not exist. In the case of hydrogen groups, these hydrocarbon groups may be bonded to each other to form a ring.) When the compound represented by the general formula (1) is a compound represented by the general formula (1) -A, R ¹ has an alkyl group or a substituent which may have a substituent. It is an aryl group that may be used.
When the compound represented by the general formula (1) is the general formula (1) compounds represented by -B, one of R ² and R ³ is a hydrogen atom, the other of R ² and R ³ The curable composition according to claim 3, which is an alkyl group which may have a substituent or an aryl group which may have a substituent. A compound represented by the following general formula (1).

(In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or the ester. Nitrogen that forms an amide structure with a group containing a hydrocarbon group that may have a substituent, that does not have a hydrogen atom bonded to the β-position with respect to the structure or does not have a β-position, or an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, which is bonded to the atom and the nitrogen atom, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. , A group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. It is a group represented.)

(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 independent of each other. When it is a hydrogen atom or a hydrocarbon group and ^{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, 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 2 of R ⁴¹ , R ⁴² , R ⁴³ and R ^44. When the species or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is formed for the carbon atom to which X is bonded. ing.) The compound according to claim 5, which is a compound represented by the following general formula (1) -A or a compound represented by the following general formula (1) -B.

(In the formula, R ¹ has a pKa of the hydrogen atom at the β-position with respect to the adjacent ester structure of 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent ester structure or the β-position does not exist. It is a hydrocarbon group which may have a substituent, and R ² and R ³ are independently hydrogen atoms or the pKa of the β-position hydrogen atom with respect to the adjacent amide structure is 27 or more, or are adjacent to each other. It is a hydrocarbon group which may have a substituent, in which a hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist, and X is independently the general formula (1) -11, ( 1) A group represented by -12, (1) -13 or (1) -14. At ^{least one of R 2} and R ³ has a pKa of the β-position hydrogen atom with respect to the adjacent amide structure of 27 or more. Alternatively, it is a hydrocarbon group that may have a substituent, with no hydrogen atom attached to the β-position or no β-position with respect to the adjacent amide structure. R ² and R ³ are adjacent amides. The pKa of the hydrogen atom at the β-position with respect to the structure is 27 or more, or the hydrogen atom is not bonded to the β-position with respect to the adjacent amide structure or the β-position does not exist. In the case of hydrogen groups, these hydrocarbon groups may be bonded to each other to form a ring.) When the compound represented by the general formula (1) is a compound represented by the general formula (1) -A, R ¹ has an alkyl group or a substituent which may have a substituent. It is an aryl group that may be used.
When the compound represented by the general formula (1) is the general formula (1) compounds represented by -B, one of R ² and R ³ is a hydrogen atom, the other of R ² and R ³ The compound according to claim 6, which is an alkyl group which may have a substituent or an aryl group which may have a substituent. Including the compound represented by the following general formula (1)
A 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.

(In the formula, G is bonded to an oxygen atom forming an ester structure with an adjacent carbonyl group and the oxygen atom, and the pKa of the hydrogen atom at the β-position with respect to the ester structure is 27 or more, or the ester. Nitrogen that forms an amide structure with a group containing a hydrocarbon group that may have a substituent, that does not have a hydrogen atom bonded to the β-position with respect to the structure or does not have a β-position, or an adjacent carbonyl group. The pKa of the hydrogen atom at the β-position with respect to the amide structure is 27 or more, which is bonded to the atom and the nitrogen atom, or the hydrogen atom is not bonded to the β-position with respect to the amide structure or the β-position does not exist. , A group containing a hydrocarbon group which may have a substituent, and X is represented by the following general formulas (1) -11, (1) -12, (1) -13 or (1) -14. It is a group represented.)

(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 independent of each other. When it is a hydrogen atom or a hydrocarbon group and ^{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, 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 2 of R ⁴¹ , R ⁴² , R ⁴³ and R ^44. When the species or more are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring; the bond marked with * is formed for the carbon atom to which X is bonded. ing.) A cured product obtained by reacting the curable composition according to any one of claims 1 to 4.

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