JP7670609B2 - Carbamoyloxime compound, and polymerization initiator and polymerizable composition containing said compound - Google Patents

Description

The present invention relates to carbamoyl oxime compounds.

Generally, polymerizable compositions such as photosensitive resin compositions are made by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and can be polymerized and cured or developed by exposure to energy rays (light). Therefore, they are used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, etc.

Photopolymerization initiators are divided into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by irradiation with energy rays (light). Photoradical generators have the advantages of a fast curing speed and no active species remaining after curing, but the disadvantage is that a layer that blocks oxygen must be provided when curing thin films because curing is inhibited by oxygen. Photoacid generators have the advantage of not being inhibited by oxygen, but the disadvantage is that the acid of the active species remains, causing corrosion of metal substrates and denaturing the resin after curing. Photobase generators have attracted attention because they are less likely to cause problems such as the above-mentioned curing inhibition by oxygen and corrosion by remaining active species, but generally have the problem of low sensitivity (low curing ability) compared to photoacid generators. Photobase generators are described, for example, in Patent Documents 1 and 2.

US9594302 JP 2013-163670 A

However, conventional photobase generators have low base generation efficiency and insufficient sensitivity.
Therefore, an object of the present invention is to provide a compound having high photobase generation efficiency.

The present inventors have conducted extensive research and found that a compound having a specific structure has high photobase generation efficiency and is useful as a polymerization initiator.
That is, the present invention is a carbamoyl oxime compound represented by the following general formula (I).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II):
R ¹¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and when there are multiple R ^11s in a molecule, they may be the same or different,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in a hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² ;
R ¹² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^12s in a molecule, they may be the same or different,
<Group A> is —O—, —CO—, —COO—, —NR ¹³ —, —NR ¹³ CO— and —S—;
R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^13's are present in a molecule, they may be the same or different;
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may each independently be linked to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
At least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following general formula (II):
When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups.

(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
X ¹ represents -NR ²¹ R ²² or a group represented by the following general formula (a) or (b):
R ²¹ and R ²² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
R ²⁰ , R ²¹ and R ²² may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ ;
R ²³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^23s in the group, they may be the same or different,
<Group B> is —O—, —CO—, —COO—, —NR ²⁴ —, —NR ²⁴ CO— and —S—;
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present in the group, they may be the same or different;
R ²¹ and R ²² may be bonded to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom;
n represents 0 or 1;
* represents a bond.)

⁽ In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R 38 , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>,
R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ ;
R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁴¹ is present in the group, they may be the same or different.
<Group C> is —O—, —CO—, —COO—, —NR ⁴² —, —NR ⁴² CO— and —S—;
R ⁴² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^42s are present in the group, they may be the same or different;
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ may each independently be linked to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms;
* represents a bond.)

The present invention will be described in detail below.
The carbamoyl oxime compound of the present invention is represented by the above general formula (I). The carbamoyl oxime compound represented by the above general formula (I) has geometric isomers due to the double bond of the oxime, but these are not distinguished from each other.
In other words, in this specification, the carbamoyl oxime compound represented by the above general formula (I), as well as the compounds and example compounds which are preferred forms of the compound described later, represent a mixture of isomers or either one of them, and are not limited to the isomers of the structures shown.
Hereinafter, the carbamoyl oxime compound represented by the above general formula (I) will be simply referred to as "the compound represented by general formula (I)" or "the compound of the present invention".

Examples of halogen atoms in the above general formula (I), general formula (II), general formula (a) and general formula (b) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the hydrocarbon groups having 1 to 20 carbon atoms in the above general formula (I), general formula (II), general formula (a) and general formula (b) include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms.

Examples of the aliphatic hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and cycloalkylalkyl groups such as cyclohexylmethyl; and unsaturated aliphatic hydrocarbon groups in which the carbon-carbon single bond of these groups is replaced with a carbon-carbon double bond or a carbon-carbon triple bond.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a benzyl group, a naphthyl group, a phenanthryl group, a pyrenyl group, and a biphenyl group.

The group having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² includes a group having a structure in which one or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² and having a total of 1 to 20 carbon atoms. In addition, the group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group represented by R ¹² have been substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group includes a group having a structure in which one or more hydrogen atoms in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms have been substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and having a total of 1 to 20 carbon atoms.

Examples of the groups having 1 to 20 carbon atoms in which methylene groups in a hydrocarbon group are substituted with a divalent group selected from the above <Group A>, represented by R ¹ to R ¹² , include groups in which one or more methylene groups in the above hydrocarbon group having 1 to 20 carbon atoms are substituted with -O-, -CO-, -COO-, -NR ¹³ -, -NR ¹³ CO- or -S-, and which have a total of 1 to 20 carbon atoms.

The group having 1 to 20 carbon atoms represented by R ²⁰ to R ²² in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ includes a group in which one or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ and the total number of carbon atoms is 1 to 20. In addition, the group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group represented by R ²³ have been substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group includes a group having a structure in which one or more hydrogen atoms in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms have been substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and having a total of 1 to 20 carbon atoms.

Examples of the groups having 1 to 20 carbon atoms in which methylene groups in a hydrocarbon group are substituted with a divalent group selected from the above <Group B>, represented by R ²⁰ to R ²³ , include groups in which one or more methylene groups in the above hydrocarbon group having 1 to 20 carbon atoms are substituted with -O-, -CO-, -COO-, -NR ²⁴ -, -NR ²⁴ CO- or -S-, and the total number of carbon atoms is 1 to 20.

The group having 1 to 20 carbon atoms and in which one or more hydrogen atoms in the hydrocarbon group represented by R ³¹ to R ⁴⁰ have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ includes a group having a structure in which one or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ and having a total of 1 to 20 carbon atoms.

Examples of the groups having 1 to 20 carbon atoms in which methylene groups in a hydrocarbon group are substituted with a divalent group selected from the above <Group C>, represented by R ³¹ to R ⁴⁰ , include groups in which one or more methylene groups in the above hydrocarbon group having 1 to 20 carbon atoms are substituted with -O-, -CO-, -COO-, ^-NR -, ^-NR CO- or -S-, and the total number of carbon atoms is 1 to 20.

Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms in the above general formula (I) include groups containing a tetrahydrofuranyl group, a dioxolanyl group, a tetrahydropyranyl group, a morpholyl group, a furanyl group, a thiophenyl group, a methylthiophenyl group, a hexylthiophenyl group, a benzothiophenyl group, a pyrrolyl group, a pyrrolidinyl group, an imidazolyl group, an imidazolinyl group, an imidazolidinyl group, a pyrazolinyl group, a pyrazolidinyl group, a piperidinyl group, and a piperazinyl group.

In addition, the heterocycle-containing group having 2 to 20 carbon atoms may have a substituent such as a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵⁰ , -COOR ⁵⁰ , -CO-R ⁵⁰ or -SR ^50, and may contain a structure such as -O-, -CO-, -COO-, -NR ⁵¹ -, -NR ⁵¹ CO- or -S-.
Here, R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵⁰ and R ⁵¹ is the same as the hydrocarbon group having 1 to 20 carbon atoms in the above general formula (I), the above general formula (II), the above general formula (a) and the above general formula (b).

In the above general formula (I), ^R1 and ^R2 , ^R2 and ^R3 , ^R3 and ^R4 , ^R4 and ^R5 , ^R6 and ^R7 , ^R7 and ^R8 , ^R8 and ^R9 , and R9 and ^R10 are bonded together to form a ring having ³ to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms, and examples of the ring include a benzene ring, a cyclohexene ring, a cyclohexane ring, a cyclopentadiene ring, and a cyclopentane ring. These rings may have a substituent, and examples of the substituent in this case include the substituents that may be possessed by the above heterocycle-containing group having 2 to 20 carbon atoms.

In the above general formula (II), the above general formula (a), and the above general formula (b), R ²¹ and R ²² , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ are bonded together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, and examples of the ring including the bonded nitrogen atom include a pyrrole ring, a pyrrolidine ring, an imidazole ring, an imidazolidine ring, an imidazoline ring, a pyrazole ring, a pyrazolidine ring, a piperidine ring, and a piperazine ring. These rings may have a substituent, and in this case, examples of the substituent include the substituent that the heterocycle-containing group having 2 to 20 carbon atoms may have.

In the above general formula (II), the above general formula (a), and the above general formula (b), R ²¹ and R ²² , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ are bonded together to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom, and examples of the ring including the bonded nitrogen atom include a morpholine ring, an oxazole ring, an oxazoline ring, and an oxadiazole ring. These rings may have a substituent, and examples of the substituent in this case include the substituents that may be possessed by the above heterocyclic ring-containing group having 2 to 20 carbon atoms.

In the present invention, a carbamoyloxime compound in which either or both of ^R3 and ^R8 in general formula (I) are groups represented by general formula (II) is preferred, because they are easy to synthesize, have high storage stability, and have high base generation efficiency.

A carbamoyloxime compound in which at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (I) other than the group represented by the general formula (II) is -CO-R ¹¹ is preferred because the polymerizable composition obtained is cured at a low exposure dose. In particular, a carbamoyloxime compound in which R ⁸ is a group represented by the general formula (II) and R ³ is -CO-R ¹¹ is preferred because it is easy to synthesize and has high storage stability. In this case, R ¹¹ is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms because the polymerizable composition obtained is cured at a low exposure dose, and more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic ring-containing group having 2 to 10 carbon atoms. In particular, R ¹¹ is preferably a phenyl group, a tolyl group, a mesityl group, a benzofuranyl group, or a thienyl group.

Carbamoyloxime compounds in which at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in general formula (I) other than the group represented by general formula (II) is a nitro group are also preferred because the resulting polymerizable composition is cured at a low exposure dose. In particular, carbamoyloxime compounds in which R ⁸ is a group represented by general formula (II) and R ³ is a nitro group are preferred.

Carbamoyloxime compounds in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, —CO—R ¹¹ , a nitro group, or the above general formula (II) are preferred because they have high base generation efficiency.

In addition, a carbamoyloxime compound in which X ¹ in general formula (II) is -NR ²¹ R ²² is preferred because it has high base generation efficiency, and it is more preferred that R ²¹ and R ²² are linked together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms.
In particular, it is preferable that R ²¹ and R ²² are linked together to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, and it is more preferable that they form a piperidine ring or a pyrrolidine ring.

In addition, in the carbamoyloxime compound in which X ¹ in the general formula (II) is -NR ²¹ R ²² , it is also preferable that R ²¹ is a hydrogen atom, R ²² is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and that both R ²¹ and R ²² are aliphatic hydrocarbon groups having 1 to 20 carbon atoms, because the base generation efficiency is high.

Carbamoyloxime compounds in which n is 0 in the above general formula (II) are preferred because they have high thermal stability.
A carbamoyloxime compound in which n is 1 in the above general formula (II) is preferred because the resulting polymerizable composition is cured at a low exposure dose.

Specific examples of the carbamoyl oxime compound represented by the above general formula (I) include the compounds represented by the following chemical formulas (1) to (62). However, the present invention is not limited in any way by the following compounds.

The method for producing the carbamoyloxime compound of the present invention represented by the above general formula (I) is not particularly limited. For example, when R ⁸ in general formula (I) is a group represented by general formula (II), X ¹ is -NR ²¹ R ²² , and n=0, the compound can be produced by the following method according to the following reaction formula 1.
That is, a known ketone compound is reacted with hydroxylamine hydrochloride in the presence of a base such as pyridine to obtain an oxime compound, which is then reacted with 4-nitrophenyl chloroformate and then with an amine to obtain the carbamoyl oxime compound of the present invention.

(In the formula, R ¹ to R ¹⁰ and R ²⁰ to R ²² are the same as those in the above general formula (I).)

The above reaction formula 1 shows the case where X ¹ is -NR ²¹ R ²² , but by changing the amine used, it is also possible to produce a compound in which X ¹ is a group represented by the above general formula (a) or (b).
In addition, the above reaction formula 1 shows the case where R ⁸ in general formula (I) is a group represented by general formula (II). However, by using a ketone compound having a ketone group introduced at any position other than R ⁸ as a raw material, a compound having a group represented by general formula (II) introduced at a position other than R ⁸ can also be obtained.
The oxime compound can also be produced by the method described in Japanese Patent No. 4223071.

The carbamoyl oxime compound of the present invention efficiently generates bases and radicals when irradiated with light such as ultraviolet light or when heated, and is therefore useful as a latent base generator and polymerization initiator, and is particularly useful as a latent base generator.

The latent base generator of the present invention refers to a composition containing a compound that has the function of efficiently generating a base when irradiated with light such as ultraviolet light, and its applications include a pH adjuster and a catalyst that utilizes a base.

Furthermore, among the above-mentioned polymerization initiators, the carbamoyl oxime compound of the present invention is useful as a photobase generator and photoradical polymerization initiator because it has a high efficiency of generating bases and radicals by light irradiation, and is particularly useful as a photobase generator because it has an extremely high efficiency of generating bases.

The polymerization initiator of the present invention contains at least one carbamoyl oxime compound represented by the above general formula (I). Polymerization initiators that can be used in combination with the carbamoyl oxime compound represented by the above general formula (I) are not particularly limited, but include conventionally known photobase generators and photoradical polymerization initiators.

The content of the compound represented by the above general formula (I) in the above polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass, since the resulting polymerizable composition is cured with a low exposure dose.

The polymerizable composition of the present invention contains a polymerization initiator (A) containing at least one carbamoyloxime compound represented by the above general formula (I), and a polymerizable compound (B).
The content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the polymerizable compound (B), since the resulting polymerizable composition is cured at a low exposure dose. The content of the polymerization initiator (A) of 1 part by mass or more is preferable because it is easy to prevent poor curing due to insufficient curing sensitivity, and the content of 20 parts by mass or less is preferable because it is possible to suppress volatile matters during light irradiation or heating.

The polymerizable compound (B) used in the present invention includes a compound having an anionically polymerizable functional group, a compound that cures by a reaction in which a base acts as a catalyst or a reaction in which a base is added, and a radically polymerizable compound. A photosensitive resin that cures by polymerization upon irradiation with energy rays such as ultraviolet rays, or a curable resin that has a low curing temperature, is preferable because the resulting polymerizable composition cures with a low exposure dose. The anionically polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by active energy rays such as ultraviolet rays, and examples of such a functional group include an epoxy group, an episulfide group, a cyclic monomer (σ-valerolactone, ε-caprolactam), a malonic acid ester, and the like. Examples of the reaction in which a base acts as a catalyst or in which a base is added include a urethane bond forming reaction between an isocyanate and an alcohol, an addition reaction between an epoxy resin and a compound containing a hydroxyl group, an addition reaction between an epoxy resin and a compound containing a carboxylic acid group, an addition reaction between an epoxy resin and a thiol compound, a Michael addition reaction of a (meth)acrylic group, a dehydration condensation reaction of a polyamic acid, and a hydrolysis/polycondensation reaction of an alkoxysilane.

Examples of compounds having an anionically polymerizable functional group include epoxy resins, oxetane resins, episulfide resins, cyclic amides (lactam compounds), cyclic esters (lactone compounds), cyclic carbonate compounds, malonic acid esters, etc. Examples of compounds that harden by a reaction in which a base acts as a catalyst or a reaction in which a base is added include polyamide resins (polyimide formation reaction by dehydration cyclization), epoxy-hydroxyl systems (ring-opening addition reaction), epoxy-carboxylic acid systems (ring-opening addition reaction), epoxy-thiol systems (ring-opening addition reaction), epoxy-acid anhydride systems (ring-opening polycondensation), cyanate esters (triazine cyclization reaction), cyanate ester-epoxy systems (cyclization reaction), cyanate ester-maleimide systems (crosslinking copolymerization), oxetane-hydroxyl systems (ring-opening addition reaction), oxetane-carboxylic acid systems (ring-opening addition reaction), oxetane-thiol systems (ring-opening addition reaction), oxetane-acid anhydride systems (ring-opening polycondensation), ethylene oxides (ethylene oxides ... Examples of the resins include bisulfide-hydroxyl group-based (ring-opening addition reaction), episulfide-carboxylic acid-based (ring-opening addition reaction), episulfide-thiol-based (ring-opening addition reaction), episulfide-acid anhydride-based (ring-opening polycondensation), acrylic-thiol-based (Michael addition reaction), methacrylic-thiol-based (Michael addition reaction), acrylic-amine-based (Michael addition reaction), methacrylic-amine-based (Michael addition reaction), carboxylic acid-hydroxyl group-based (polyesterification reaction), carboxylic acid-amine-based (polyamidation reaction), isocyanate-hydroxyl group-based (polyurethane-forming reaction), isocyanate-thiol-based (polythiourethane-forming reaction), and alkoxysilane-based (hydrolysis and polycondensation). Examples of the compound that polymerizes by radicals include ethylenically unsaturated compounds. It is preferable to use a compound that polymerizes by radical polymerization because of its high reactivity. These resins may be used alone or in combination of two or more. Preferred combinations include a combination of an epoxy resin and a phenol resin, which allows the reaction to proceed quickly and provides good adhesion; a combination of an epoxy resin and a thiol compound, which provides excellent low-temperature curing properties; and a combination of an ethylenically unsaturated compound and a thiol compound, which provides high reactivity.

The epoxy resin may have an epoxy group, but does not include the carbamoyl oxime compound of the present invention. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene bis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl) polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac, and terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adducts. polyglycidyl ethers of polyhydric alcohols such as those mentioned above; glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and the like, and homopolymers or copolymers of glycidyl methacrylate; glycidyl esters of N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl orthotoluidine, and the like. Epoxy compounds having an amino group; epoxidized products of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymers, and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be internally crosslinked with a prepolymer of terminal isocyanate or may be polymerized with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate, etc.).
Among the above epoxy resins, those having a glycidyl group are preferred, and those having di- or higher-functional glycidyl groups are more preferred, in terms of excellent curability of the resulting polymerizable composition.

The phenolic resin may have a phenolic hydroxyl group, but does not include the carbamoyl oxime compound and the epoxy resin. As the phenolic resin, a phenolic resin having two or more hydroxyl groups in one molecule is preferred because the resulting polymerizable composition has excellent curing properties, and generally known phenolic resins can be used. Examples of phenolic resins include bisphenol A type phenolic resins, bisphenol E type phenolic resins, bisphenol F type phenolic resins, bisphenol S type phenolic resins, phenol novolac resins, bisphenol A novolac type phenolic resins, glycidyl ester type phenolic resins, aralkyl novolac type phenolic resins, biphenyl aralkyl type phenolic resins, cresol novolac type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolac resins, polyfunctional naphthol resins, anthracene type phenolic resins, naphthalene skeleton modified novolac type phenolic resins, phenol aralkyl type phenolic resins, naphthol aralkyl type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic phenolic resins, polyol type phenolic resins, phosphorus-containing phenolic resins, polymerizable unsaturated hydrocarbon group-containing phenolic resins, and hydroxyl group-containing silicone resins, but are not particularly limited. These phenolic resins can be used alone or in combination of two or more.

The thiol compound may have a thiol group, but excludes the carbamoyloxime compounds, epoxy resins, and phenolic resins. Among the thiol compounds, those having two or more thiol groups in one molecule are preferred because the resulting polymerizable composition has excellent curability.
Specific preferred examples of the thiol compound include bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythrithiol, 1,1,3,3-tetrakis(mercaptomethyl) Examples of the mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane include 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate, and more preferably, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol thiol, bis(2-mercaptoethyl)sulfide, 2,5-bis(2-mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,3-bis(mercaptomethyl)benzene, pentaerythritol tetrakismercaptopropionate, and pentaerythritol tetrakisthioglycolate.
Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythrithiol, bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
The thiol compounds can be used alone or in combination of two or more.

Examples of the polyamide resin include resins made from acid dianhydrides such as ethylene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2,3,3-biphenyl tetracarboxylic anhydride, and 1,4,5,8-naphthalene tetracarboxylic dianhydride, and diamines such as (o-, m-, or p-)phenylenediamine, (3,3'- or 4,4'-)diaminodiphenyl ether, diaminobenzophenone, and (3,3'- or 4,4'-)diaminodiphenylmethane.

Examples of the polyurethane resin include resins made from polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate, and polyols (polyfunctional alcohols) such as polyether polyols, polyester polyols, and polycarbonate polyols.
Examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryllactam.
Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

The ethylenically unsaturated compound may have an ethylenically unsaturated bond, but excludes the carbamoyl oxime compounds, epoxy resins, phenolic resins, and thiol compounds. Examples of the ethylenically unsaturated compound include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], and ω-carboxypolycaprolactone mono(meth)acrylate; unsaturated polybasic acids such as hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, Stearyl acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di (meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloyl)acrylate, esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as [triloylethyl]isocyanurate and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate; acids of unsaturated polybasic acids, such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylhimic anhydride. Anhydrides; amides of unsaturated monobasic acids and polyamines such as (meth)acrylamide, methylene bis-(meth)acrylamide, diethylenetriamine tris(meth)acrylamide, xylylene bis(meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl(meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, and vinyl sulfo. unsaturated aromatic compounds such as vinylbenzyl methyl ether, vinylbenzyl glycidyl ether, etc.; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine, etc.; vinyl alcohols such as allyl alcohol, crotyl alcohol, etc.; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, etc.; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc.; indenes such as indene, 1-methylindene, etc.; 1,3-butadiene, isoprene, chlo aliphatic conjugated dienes such as chloroprene; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds.
The ethylenically unsaturated compounds may be used alone or in combination of two or more.

As the above ethylenically unsaturated compound, commercially available products can be used, such as Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (all manufactured by Nippon Kayaku Co., Ltd.); Aronix M-215, M-350 (all manufactured by Toagosei Co., Ltd.); NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (all manufactured by Showa Denko Co., Ltd.); and the like.

The content of polymerizable composition (B) may be an appropriate amount depending on the intended use, but in order to prevent poor curing, it is preferable to include it in an amount of 50 parts by mass or more of the solids content (all components other than the solvent) in the polymerizable composition, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more.

The polymerizable composition of the present invention may contain optional additives such as inorganic compounds, colorants, latent epoxy curing agents, chain transfer agents, sensitizers, and solvents.

Examples of the inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder (particularly glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds are used, for example, as fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink-developing agents, etc.

The coloring materials include pigments, dyes, natural dyes, etc. These coloring materials can be used alone or in combination of two or more.

Examples of the pigments include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthranthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, metal complex compounds of azo dyes and cyanine dyes, and lake pigments. carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black; the above carbon black adjusted or coated with an epoxy resin; the above carbon black previously dispersed in a solvent with a resin to adsorb 20 to 200 mg/g of resin; the above carbon black subjected to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less; Carbon black having a total oxygen content of 9 mg or more per 100 ^m2 of surface area calculated from ₂ ; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, synthetic iron black, amber, and other organic or inorganic pigments can be used. These pigments can be used alone or in combination.

As the above pigment, commercially available pigments can be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 18 4, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1 , 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 1 14, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and these may be used in combination.

Examples of the above-mentioned latent epoxy curing agents include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl sulfone, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas, and melamine.

As the chain transfer agent or sensitizer, a compound containing a sulfur atom is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds; iodized alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid; trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthiopropionate, and the like. Examples of the thiol compounds include polyfunctional aliphatic thiol compounds such as tandiol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, Compound No. C1 shown below, and trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate; and Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko K.K.

The above-mentioned solvent is usually a solvent capable of dissolving or dispersing each of the above-mentioned components (polymerization initiator (A) and polymerizable compound (B), etc.), for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc.; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid, etc. ester-based solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; lactone-based solvents such as γ-caprolactone, δ-caprolactone, and γ-butyrolactone; cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.) ) and other paraffin-based solvents; halogenated aliphatic hydrocarbon-based solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon-based solvents such as chlorobenzene; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide; water, and the like can be used alone or in combination of two or more of them.
Among these, from the viewpoints of alkaline developability, patterning ability, film-forming ability, and solubility, ketones or ether ester solvents, in particular, propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as "PGMEA") or cyclohexanone are preferably used.
In the polymerizable composition of the present invention, the content of the solvent is not particularly limited as long as each component is uniformly dispersed or dissolved and the polymerizable composition of the present invention exhibits a liquid or paste state suitable for each application. However, it is usually preferable to contain the solvent in such a range that the amount of solids in the polymerizable composition of the present invention (all components other than the solvent) is 10 to 90 mass %, since a uniform cured product can be obtained.

Furthermore, the polymerizable composition of the present invention can improve the properties of the cured product by using an organic polymer, such as polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, etc.
When the organic polymer is used, the content thereof is preferably 10 to 500 parts by mass per 100 parts by mass of the polymerizable compound (B) in order to provide an excellent curing property of the resulting polymerizable composition.

The polymerizable composition of the present invention may further contain a surfactant, a silane coupling agent, a melamine compound, etc.

Examples of the above surfactants that can be used include fluorosurfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; cationic surfactants such as higher amine halogen acid salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides; amphoteric surfactants; and silicone surfactants, which may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, silane coupling agents having an isocyanate group, a methacryloyl group or an epoxy group, such as KBE-9007, KBM-502, KBE-403, etc., are preferably used.

Examples of the melamine compound include nitrogen compounds such as (poly)methylol melamine, (poly)methylol glycol uril, (poly)methylol benzoguanamine, and (poly)methylol urea, in which all or a portion (at least two) of the active methylol groups (CH ₂ OH groups) are alkyl etherified.
Here, the alkyl group constituting the alkyl ether may be a methyl group, an ethyl group, or a butyl group, which may be the same as or different from each other. Furthermore, the methylol group that is not alkyl etherified may be self-condensed in one molecule, or may be condensed between two molecules to form an oligomer component.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used.
Among these, alkyl-etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred from the viewpoints of solubility in a solvent and resistance to crystallization from the polymerizable composition.

In the polymerizable composition of the present invention, the content of optional components other than the polymerization initiator (A) and the polymerizable compound (B) (excluding inorganic compounds, colorants, and solvents) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total per 100 parts by mass of the polymerizable compound (B) in order to provide an obtained polymerizable composition with excellent curing properties.

The polymerizable composition of the present invention can be irradiated with energy rays to form a cured product. The cured product is formed into an appropriate shape depending on the application. For example, when forming a film-like cured product, the polymerizable composition of the present invention can be applied to a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, or plastic by known means such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, or immersion. In addition, once applied to a support substrate such as a film, it can also be transferred to another support substrate, and there is no limitation on the application method.

The light source of the energy rays used when curing the polymerizable composition of the present invention can be electromagnetic wave energy having a wavelength of 2000 angstroms to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., as well as high energy rays such as electron beams, X-rays, and radiation. However, because the resulting polymerizable composition has excellent curing properties, it is preferable to use ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm.

Furthermore, a direct laser writing method in which an image is formed directly from digital information from a computer or the like without using a mask by using a laser beam as an exposure light source is useful because it not only improves productivity but also improves resolution and positional accuracy. As the laser beam, light with a wavelength of 340 to 430 nm is preferably used, but lasers that emit light in the visible to infrared region, such as excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, and YAG lasers, can also be used. When using these laser beams, a sensitizing dye that absorbs light in the relevant visible to infrared region is preferably added because the resulting polymerizable composition has excellent curability.

In addition, in order to harden the polymerizable composition of the present invention, heating is usually required after irradiation with the above-mentioned energy rays, and heating to about 40 to 150°C is preferred in terms of the hardening rate.

The polymerizable composition of the present invention is useful in the manufacture of photocurable paints or varnishes; photocurable adhesives; coatings for metals; printed circuit boards; color filters in liquid crystal display elements for color displays such as color televisions, PC monitors, personal digital assistants, and digital cameras; color filters in CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; printing plates; adhesives; dental compositions; gel coats; photoresists for electronics; electroplating resists; etching resists; dry films; solder resists; resists for producing color filters for various display applications or for forming the structures thereof in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; and resists for encapsulating electrical and electronic components. the like, and there is no particular limitation on the uses thereof.

The polymerizable composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for the purpose of forming protrusions for vertical alignment type liquid crystal display elements. It is particularly useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertical alignment type liquid crystal display elements.

The above-mentioned spacer for liquid crystal display panels is preferably formed by the steps of (1) forming a coating film of the polymerizable composition of the present invention on a substrate, (2) irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, (3) baking after exposure, (4) developing the coating after exposure, and (5) heating the coating after development.

The polymerizable composition of the present invention to which a coloring material has been added is preferably used as a resist constituting each pixel of RGB, etc. in a color filter, or as a black matrix resist forming the partition walls of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent agent has been added, it is preferably used for partition walls for inkjet color filters having a profile angle of 50° or more. As the ink repellent agent, a fluorosurfactant or a composition containing a fluorosurfactant is preferably used.

When used as a partition for an inkjet color filter, the partition formed from the polymerizable composition of the present invention partitions the surface of a transfer recipient, and an optical element is manufactured by a method in which droplets are applied by an inkjet method to recesses on the partitioned transfer recipient to form image areas. In this case, it is preferable that the droplets contain a colorant and the image areas are colored. In that case, the optical element manufactured by the above manufacturing method has at least a pixel group consisting of a plurality of colored areas on a substrate and partitions separating each colored area of the pixel group.

The polymerizable composition of the present invention can also be used as a protective film or insulating film composition. In this case, it can contain an ultraviolet absorber, alkylated modified melamine and/or acrylic modified melamine, mono- or di-functional (meth)acrylate monomer containing an alcoholic hydroxyl group in the molecule, and/or silica sol.

The insulating film is used in an insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable supporting substrate, the laminate can be developed with an alkaline aqueous solution, and it is preferable that the insulating resin layer has a film thickness of 10 to 100 μm.

The polymerizable composition of the present invention can be used as a photosensitive paste composition by incorporating an inorganic compound. The photosensitive paste composition can be used to form fired patterns such as partition patterns, dielectric patterns, electrode patterns, and black matrix patterns of plasma display panels.

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The fact that the compounds obtained below are "liquid" means that they are liquid at atmospheric pressure and 25°C.

Example 1 Synthesis of Compound 1 Compound 1 was synthesized according to the scheme shown below.

(Synthesis of oxime body 1)
In a 100 ml four-neck flask, 1.0 eq. of 2-(4-((4-(2-methylbenzoyl)phenyl)thiol)phenyl)acetonitrile and 1.0 eq. of sodium hydroxide were added and dissolved in ethanol (100% by weight of the theoretical yield), and the mixture was stirred on an ice bath at 5° C. Then, 1.0 eq. of isobutyl nitrite dissolved in ethanol (100% by weight of the theoretical yield) was added dropwise. The reaction solution was returned to room temperature and stirred for 2 hours, then filtered and the filtrate was concentrated. Ethyl acetate was added thereto, and the mixture was washed three times with ion-exchanged water, dried over magnesium sulfate, and concentrated again. The residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane=1:5) to obtain the target product as a brown viscous liquid compound in a yield of 60%.

(Synthesis of Compound 1)
In a 100 ml four-neck flask, 1.0 eq. of oxime body 1, dichloromethane (500% by weight of theoretical yield), and 2.0 eq. of triethylamine were added and stirred on an ice bath at 5°C. 1.1 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 5°C again on an ice bath, 1.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 3 hours, and the solvent was distilled off under reduced pressure. Ethyl acetate and a 5% by mass aqueous NaOH solution were added thereto, and oil-water separation was performed. The organic layer was further washed three times with ion-exchanged water, and then concentrated. Ethanol was added to the residue to perform crystallization, and the target product was obtained as a pale yellow powdery compound in a yield of 79%. The obtained compound was subjected to TG-DTA (melting point) measurement and ¹ H-NMR measurement. The results are shown in Tables 1 and 2, respectively.

[Example 2] Synthesis of Compound 2 Compound 2 was synthesized according to the scheme shown below.

(Synthesis of oxime body 2)
Into a 100 ml four-neck flask, 1.0 eq. of 2,2,2-trifluoro-1-(4-((4-(2-methylbenzoyl)phenyl)thio)phenyl)ethan-1-one was added and dissolved in ethanol (600% by weight of the theoretical yield). 1.2 eq. of hydroxyammonium chloride and 3.0 eq. of pyridine were added to the solution. The reaction mixture was refluxed for 3 hours, and the solvent was distilled off under reduced pressure. Ion-exchanged water was added thereto, and extraction was performed with ethyl acetate. The organic layer was washed with 5% by mass hydrochloric acid and ion-exchanged water in this order, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane=1:5) to obtain the target product as a brown viscous liquid compound in a yield of 76%.

(Synthesis of Compound 2)
The same operations as in Example 1 were carried out up to the water washing step, except that oxime body 1 was changed to oxime body 2. The residue after concentration was purified by silica gel column chromatography (eluent: ethyl acetate and hexane = 1:5) to obtain the target product as a yellow viscous liquid compound in a yield of 76%. The obtained compound was subjected to ^1H -NMR measurement. The results are shown in Table 2.

[Example 3] Synthesis of compound 3 Compound 3 was synthesized according to the scheme shown below.

(Synthesis of Compound 3)
In a 100 ml four-neck flask, 1.0 eq. of oxime body 3, dichloromethane (600% by weight of theoretical yield), and 2.8 eq. of triethylamine were added and stirred on an ice bath at 0°C. 2.1 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise to the mixture. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 0°C again on an ice bath, 2.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed twice with a 1% by weight aqueous NaOH solution and three times with ion-exchanged water. The organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:3). Ethanol (1500% by weight of theoretical yield) was added thereto, and crystallization was performed, and the target product was obtained as a pale yellow powdery compound in a yield of 63%. The compound thus obtained was subjected to TG-DTA (melting point) measurement and ¹ H-NMR measurement, and the results are shown in Tables 1 and 2, respectively.

[Example 4] Synthesis of compound 4 Compound 4 was synthesized according to the scheme shown below.

(Synthesis of oxime 4)
In a 100 ml four-neck flask, 1.0 eq. of 1-(4-((4-nitrophenyl)thio)phenyl)dodecan-1-one was added and dissolved in dimethylformamide (300% by weight of the theoretical yield). 3.2 eq. of hydroxyammonium chloride and 3.2 eq. of sodium hydroxide were added to the solution. The reaction mixture was heated and stirred at 65° C. for 2 hours, ion-exchanged water was added, and the mixture was extracted with ethyl acetate. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:10). As a result, the target product was obtained as a pale yellow solid compound in a yield of 61%.

(Synthesis of Compound 4)
In a 100 ml four-neck flask, 1.0 eq. of oxime 4, dichloromethane (600% by weight of theoretical yield), and 2.0 eq. of triethylamine were added and stirred on an ice bath at 0° C. Then, 1.3 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 0° C. again on an ice bath, 1.3 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed twice with a 1% by mass aqueous NaOH solution and three times with ion-exchanged water. The organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:5). As a result, the target product was obtained as a light brown liquid compound in a yield of 72%. ¹ H-NMR measurement of the obtained compound was performed. The results are shown in Table 2.

[Example 5] Synthesis of compound 5 Compound 5 was synthesized according to the scheme shown below.

(Synthesis of oxime 5)
Into a 100 ml four-neck flask, 1.0 eq. of 1-(4-((4-nitrophenyl)thio)phenyl)dodecan-1-one was added and dissolved in THF (350% by weight of the theoretical yield). 1.0 eq. of 4M HCl-ethyl acetate and 1.2 eq. of isobutyl nitrite were added thereto and stirred at 35°C for 3 hours. Methyl isobutyl ketone was added to the reaction solution, which was then washed six times with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:8). As a result, the target product was obtained as a light brown liquid compound in a yield of 86%.

(Synthesis of Compound 5)
The same operations as in Example 1 were carried out up to the water washing step, except that oxime body 1 was changed to oxime body 5. The mixture was concentrated to obtain the target product as a brown liquid compound in a yield of 41%. The obtained compound was subjected to ^1H -NMR measurement. The results are shown in Table 2.

[Example 6] Synthesis of compound 6 Compound 6 was synthesized according to the scheme shown below.

(Synthesis of Compound 6)
The same operations as in Example 1 were carried out up to the water washing step, except that oxime body 1 was replaced with oxime body 5 and piperidine was replaced with n-dibutylamine. This was concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:7). As a result, the target substance was obtained as a pale yellow liquid compound in a yield of 28%. The obtained compound was subjected to ¹ H-NMR measurement. The results are shown in Table 2.

[Example 7] Synthesis of compound 7 Compound 7 was synthesized according to the scheme shown below.

(Synthesis of oxime 6)
Into a 100 ml four-neck flask, 1.0 eq. of 1-(4-((4-(thiophene-2-carbonyl)phenyl)thio)phenyl)ethan-1-one was added and dissolved in dimethylformamide (400% by weight of the theoretical yield). 1.1 eq. of hydroxyammonium chloride and 1.1 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 55° C. for 2 hours. Ethyl acetate (400% by weight of the theoretical yield) was added to the reaction solution, and ion-exchanged water (800% by weight of the theoretical yield) was added dropwise to carry out crystallization, obtaining the target product in a yield of 89%.

(Synthesis of Compound 7)
In a 100 ml four-neck flask, 1.0 eq. of oxime body 6, dichloromethane (600% by weight of theoretical yield), and 2.0 eq. of triethylamine were added, and the mixture was stirred on an ice bath at 0° C. Then, 1.5 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling to 0° C. again on an ice bath, 1.5 eq. of n-dibutylamine was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed twice with a 1% by mass aqueous NaOH solution and three times with ion-exchanged water. The organic layer was dried and concentrated with magnesium sulfate, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:15). As a result, the target product was obtained as a pale yellow solid compound in a yield of 59%. The obtained compound was subjected to TG-DTA (melting point) measurement and ¹ H-NMR measurement. The results are shown in Tables 1 and 2, respectively.

[Example 8] Synthesis of compound 8 Compound 8 was synthesized according to the scheme shown below.

(Synthesis of oxime 7)
Into a 100 ml four-neck flask, 1.0 eq. of 3-cyclohexyl-1-(4-((4-(2-methylbenzoyl)phenyl)thio)phenyl)propan-1-one was added and dissolved in dimethylformamide (300% by weight of theoretical yield). 1.1 eq. of hydroxyammonium chloride and 1.1 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 60° C. for 3 hours, ion-exchanged water was added, and the mixture was extracted with ethyl acetate. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:8). As a result, the target product was obtained as a pale yellow solid compound in a yield of 60%.

(Synthesis of Compound 8)
The same operations as in Example 1 were carried out up to the water washing step, except that oxime body 1 was changed to oxime body 7. The resulting mixture was concentrated to obtain the target product as a light brown liquid compound in a yield of 50%. The compound obtained was subjected to ¹ H-NMR measurement. The results are shown in Table 2.

Comparative Example 1 Synthesis of Comparative Compound 1 Comparative compound 1 was synthesized according to the scheme shown below.

(Synthesis of Comparative Compound 1)
Except for changing n-dibutylamine to n-butylamine, the same operations as in Example 7 were carried out up to the water washing step. This was concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:8). As a result, the target substance was obtained as a pale yellow solid compound in 81% yield. The obtained compound was subjected to TG-DTA (melting point) measurement and ¹ H-NMR measurement. The results are shown in Tables 1 and 2, respectively.

[Examples 9 and 10 and Comparative Examples 2 and 3] Preparation of polymerizable compositions Polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2 were obtained by carrying out the blending procedures shown in Table 3. The blending values in the table indicate parts by mass.
The symbols of each component in the table represent the following components.
A-1: Compound 3
A-2: Compound 5
A'-3: Comparative compound 1
A'-4: Comparative compound 2
B-1: EPPN-201 (phenol novolac type epoxy resin, epoxy equivalent 193 g/eq., manufactured by Nippon Kayaku Co., Ltd.)
B-2: H-3M (phenolic resin, hydroxyl equivalent weight 105 to 109 g/eq., manufactured by Meiwa Kasei Co., Ltd.)
C-1: FZ-2122 (polyether modified polysiloxane, manufactured by Dow Corning Toray Co., Ltd., 1 wt% PGMEA solution)
D-1: Cyclopentanone (solvent)

[Evaluation Examples 1 and 2 and Comparative Evaluation Examples 1 and 2]
The presence or absence of residual film was confirmed by the following procedure for the cured products of the polymerizable compositions 1 and 2 and the comparative polymerizable compositions 1 and 2. The results are shown in Table 5.
Polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2 (coating amount: about 2 mL) were each coated on a glass substrate (10 cm x 10 cm) using a spin coater (500 rpm x 2 seconds -> 1000 rpm x 10 seconds -> slope x 0.5 seconds), and prebaked in an oven (90°C x 90 seconds) to form a film.
Each film was masked with a step tablet (33-step type, OD value 0-3, Table 4) having a gradation of continuously changing transmittance, and irradiated with a predetermined amount of ultraviolet light using a UV-LED (365 nm) (illuminance 20 mW/cm ² , exposure time 150 seconds, cumulative exposure amount 3000 mJ/cm ² ).
After the exposure, the resist was post-baked in an oven (100° C.×20 minutes), developed (PGMEA, 30 seconds) and rinsed (isopropyl alcohol, 10 seconds).
The number of remaining steps of the obtained cured film sample was visually confirmed. The number of remaining steps means the maximum number of steps in which the cured film remains. The transmittance was determined from the number of remaining steps according to Table 4, and the converted sensitivity was calculated using the following formula.
Converted sensitivity (mJ/cm ² ) = cumulative exposure amount (3000mJ/cm ² ) x transmittance (%)
The remaining plate number and converted sensitivity are shown in Table 5.

From the results in Table 5 above, the polymerizable composition containing the carbamoyl oxime compound of the present invention has a larger number of remaining steps (higher curability) than the comparative polymerizable composition, and therefore has a high photobase generation efficiency, can be cured with a low exposure dose, and is highly sensitive to a UV-LED light source. Therefore, it is clear that the compound of the present invention is an excellent polymerization initiator.

[Example 11] Synthesis of compound 9 Compound 9 was synthesized according to the scheme shown below.

(Synthesis of oxime 8)
In a 100 ml four-neck flask, 1.0 eq. of 1,1'-(thiobis(4,1-phenylene))bis(hexan-1-one) was added and dissolved in dimethylformamide (400% by weight of the theoretical yield). 2.6 eq. of hydroxyammonium chloride and 2.6 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 55°C for 7 hours, after which ion-exchanged water was added and the mixture was extracted with ethyl acetate. The organic layer was washed three times with ion-exchanged water, dried over magnesium sulfate, and concentrated. 1,2-dichloroethane (12,000% by weight of the theoretical yield) was added thereto and recrystallized to obtain the target product as a white powder in a yield of 77%.

(Synthesis of Compound 9)
In a 100 ml four-neck flask, 1.0 eq. of oxime 8, dichloroethane (600% by weight of theoretical yield), and 4.0 eq. of triethylamine were added and stirred on an ice bath at 5°C. 3.0 eq. of 4-nitrophenyl chloroformate dissolved in dichloroethane (300% by weight of theoretical yield) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling to 5°C again on an ice bath, 3.0 eq. of aniline was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto, and oil-water separation was performed. The organic layer was further washed three times with a 1% by weight aqueous sodium hydroxide solution and twice with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:25), and the target product was obtained as a white powdery compound in a yield of 57%. The resulting compound was subjected to TG-DTA (melting point) measurement and ¹ H-NMR measurement, and the results are shown in Tables 6 and 7, respectively.

[Example 12] Synthesis of compound 10 Compound 10 was synthesized according to the scheme shown below.

(Synthesis of Compound 10)
Except for changing aniline to 4-methylpiperidine, the same operations as in Example 11 were carried out up to the water washing step. The residue after concentration was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:5) to obtain the target product as a pale yellow viscous liquid compound in 80% yield. The obtained compound was subjected to ¹ H-NMR measurement. The results are shown in Table 7.

[Example 13] Synthesis of compound 11 Compound 11 was synthesized according to the scheme shown below.

(Synthesis of oxime 9)
1.0 eq. of 1,1'-(thiobis(4,1-phenylene))bis(hexan-1-one) was added to a 100 ml four-neck flask and dissolved in dimethylformamide (350% by weight of theoretical yield). 2.0 eq. of 4M HCl-ethyl acetate and 2.5 eq. of isobutyl nitrite were added thereto and stirred at 45°C for 3 hours. Ethyl acetate was added to the reaction solution, which was washed four times with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:5) to obtain the target product as a pale yellow solid in a yield of 72%.

(Synthesis of Compound 11)
The same operations as in Example 11 were carried out up to the water washing step, except that oxime body 1 was replaced with oxime body 9 and aniline was replaced with dibutylamine. The residue after concentration was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:20) to obtain the target product as a pale yellow viscous liquid compound in a yield of 5%. The obtained compound was subjected to ¹ H-NMR measurement. The results are shown in Table 7.

The carbamoyloxime compound of the present invention has high photobase generation efficiency, and when used as a polymerization initiator, it can generate a base more efficiently than conventional photobase generators, and therefore can cure a polymerizable compound even at a low exposure dose. In particular, when used in a curable resin composition containing an epoxy resin or a phenol resin, it shows high curability.

Claims (18)

A carbamoyl oxime compound represented by the following general formula (I):
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II):
R ⁸ represents a group represented by the following general formula (II):
one or more of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ is a nitro group;
R ¹¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and when there are multiple R ^11s in a molecule, they may be the same or different,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in a hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² ;
R ¹² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^12s in a molecule, they may be the same or different,
<Group A> is —O—, —CO—, —COO—, —NR ¹³ —, —NR ¹³ CO— and —S—;
R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^13's are present in a molecule, they may be the same or different;
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁹ and R ¹⁰ may each independently be linked to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups.
(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
X ¹ represents -NR ²¹ R ²² or a group represented by the following general formula (a) or (b):
R ²¹ and R ²² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
R ²⁰ , R ²¹ and R ²² may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ ;
R ²³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^23s in the group, they may be the same or different,
<Group B> is —O—, —CO—, —COO—, —NR ²⁴ —, —NR ²⁴ CO— and —S—;
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present in the group, they may be the same or different;
R ²¹ and R ²² may be bonded to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom;
n represents 0 or 1;
* represents a bond.)
⁽ In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R 38 , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>,
R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ ;
R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁴¹ is present in the group, they may be the same or different;
<Group C> is —O—, —CO—, —COO—, —NR ⁴² —, —NR ⁴² CO— and —S—;
R ⁴² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^42s are present in the group, they may be the same or different;
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ may each independently be linked to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms;
* represents a bond.) A carbamoyl oxime compound represented by the following general formula (I):
(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II):
R ¹¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and when there are multiple R ^11s in a molecule, they may be the same or different,
^R3 and ^R8 represent a group represented by the following general formula (II):
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ and R ¹¹ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in a hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² ;
R ¹² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^12s in a molecule, they may be the same or different,
<Group A> is —O—, —CO—, —COO—, —NR ¹³ —, —NR ¹³ CO— and —S—;
R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^13's are present in a molecule, they may be the same or different;
R ¹ and R ² , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁹ and R ¹⁰ may each independently be linked to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups.
(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
X ¹ represents -NR ²¹ R ²² or a group represented by the following general formula (a) or (b):
R ²¹ and R ²² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
R ²⁰ , R ²¹ and R ²² may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ ;
R ²³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^23s in the group, they may be the same or different,
<Group B> is —O—, —CO—, —COO—, —NR ²⁴ —, —NR ²⁴ CO— and —S—;
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present in the group, they may be the same or different;
R ²¹ and R ²² may be bonded to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom;
n represents 0 or 1;
* represents a bond.)
⁽ In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R 38 , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>,
R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ ;
R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁴¹ is present in the group, they may be the same or different;
<Group C> is —O—, —CO—, —COO—, —NR ⁴² —, —NR ⁴² CO— and —S—;
R ⁴² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^42s are present in the group, they may be the same or different;
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ may each independently be linked to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms;
* represents a bond.) A carbamoyl oxime compound represented by the following general formula (I):
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II):
R ¹¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and when there are multiple R ^11s in a molecule, they may be the same or different,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in a hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² ;
R ¹² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^12s in a molecule, they may be the same or different,
<Group A> is —O—, —CO—, —COO—, —NR ¹³ —, —NR ¹³ CO— and —S—;
R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^13's are present in a molecule, they may be the same or different;
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may each independently be linked to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
At least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following general formula (II):
When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups.
(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B> ,
<Group B> is —O—, —CO—, —COO—, —NR ²⁴ —, —NR ²⁴ CO— and —S—;
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present in the group, they may be the same or different;
X ¹ represents a group represented by -NR ²¹ R ²² ;
R ²¹ and R ²² are bonded to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom;
n represents 0 or 1;
* represents a bond.) A carbamoyl oxime compound represented by the following general formula (I):
(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II):
R ³ represents a group represented by -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ or -SR ¹¹ ;
R ⁸ represents a group represented by the following general formula (II):
R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and when there are multiple R ^11s in a molecule, they may be the same or different,
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ and R ¹¹ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in a hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² ;
R ¹² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^12s in a molecule, they may be the same or different,
<Group A> is —O—, —CO—, —COO—, —NR ¹³ —, —NR ¹³ CO— and —S—;
R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^13's are present in a molecule, they may be the same or different;
R ¹ and R ² , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁹ and R ¹⁰ may each independently be linked to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups.
(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
X ¹ represents -NR ²¹ R ²² or a group represented by the following general formula (a) or (b):
R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>,
R ²⁰ , R ²¹ and R ²² may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ ;
R ²³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and when there are multiple R ^23s in the group, they may be the same or different,
<Group B> is —O—, —CO—, —COO—, —NR ²⁴ —, —NR ²⁴ CO— and —S—;
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present in the group, they may be the same or different;
R ²¹ and R ²² may be bonded to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom;
n represents 0 or 1;
* represents a bond.)
⁽ In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R 38 , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>,
R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ ;
R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁴¹ is present in the group, they may be the same or different;
<Group C> is —O—, —CO—, —COO—, —NR ⁴² —, —NR ⁴² CO— and —S—;
R ⁴² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^42s are present in the group, they may be the same or different;
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ may each independently be linked to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms;
* represents a bond.) The carbamoyl oxime compound according to claim 3, wherein R ⁸ in the general formula (I) is a group represented by the general formula (II). The carbamoyloxime compound according to claim 2 , wherein at least one of R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ in the general formula (I) is -CO-R ¹¹ . R in general formula (I) ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ At least one of the groups is -CO-R ¹¹ The carbamoyl oxime compound according to claim 3, wherein The carbamoyl oxime compound according to claim 2 , wherein at least one of R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ in formula (I) is a nitro group. R in general formula (I) ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ The carbamoyl oxime compound according to claim 3, wherein at least one of the following is a nitro group: The carbamoyl oxime compound according to claim 1 or 3, wherein R ³ and R ⁸ in the general formula (I) are groups represented by the above general formula (II). In the general formula (II), X ¹ is —NR ²¹ R ²² ;
The carbamoyloxime compound according to claim 1 or 2, wherein R ²¹ and R ²² are linked to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom. In the general formula (II), X ¹ is —NR ²¹ R ²² ;
3. The carbamoyl oxime compound according to claim 1 or 2, wherein R ²¹ is a hydrogen atom, and R ²² is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or R ²¹ and R ²² are both aliphatic hydrocarbon groups having 1 to 20 carbon atoms. A latent base generator comprising the carbamoyl oxime compound according to any one of claims 1 to 12 . A polymerization initiator comprising the carbamoyl oxime compound according to any one of claims 1 to 12 . A polymerizable composition comprising the carbamoyl oxime compound according to any one of claims 1 to 12 and a polymerizable compound. The polymerizable composition according to claim 15, wherein the polymerizable compound is an epoxy resin or an ethylenically unsaturated compound, or a mixture containing an epoxy resin and a phenolic resin, a mixture containing an epoxy resin and a thiol compound, or a mixture containing an ethylenically unsaturated compound and a thiol compound. A cured product of the polymerizable composition according to claim 15 or 16 . A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to claim 15 or 16 with energy rays.