阅读说明：本技术 氨基甲酰肟化合物及含有该化合物的聚合引发剂及聚合性组合物 (Carbamoyloxime compound, and polymerization initiator and polymerizable composition each containing same ) 是由 友田和贵 大槻龙也 有吉智幸 冈田光裕 木村正树 于 2020-06-09 设计创作，主要内容包括：本发明的课题在于提供具有高的光产碱效率的化合物。本发明为下述通式(I)所示的氨基甲酰肟化合物。式中,R～(1)、R～(2)、R～(3)、R～(4)、R～(5)、R～(6)、R～(7)、R～(8)、R～(9)及R～(10)各自独立地表示氢原子、卤素原子、氰基、硝基或氨基甲酰肟基等,R～(1)、R～(2)、R～(3)、R～(4)、R～(5)、R～(6)、R～(7)、R～(8)、R～(9)及R～(10)中的1个以上为氨基甲酰肟基。氨基甲酸酯基可以在结构中含有由氢原子、氮原子及碳原子构成的碳原子数为2～10的环、或由氢原子、氧原子、氮原子及碳原子构成的碳原子数为2～10的环。(The present invention addresses the problem of providing a compound having high photobase efficiency. The present invention relates to a carbamoyloxime 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 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyloximino group or the like, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 And R 10 More than 1 of them are carbamoyloximido. The carbamate group may have a structure containing a ring having 2 to 10 carbon atoms and composed of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring having 2 to 10 carbon atoms and composed of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom.)

1. A carbamoyloxime compound represented by the following general formula (I),

in the formula, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR¹¹、-COOR¹¹、-CO-R¹¹、-SR¹¹A C1-20 hydrocarbon group, a C2-20 heterocyclic group, a C1-20 group in which a methylene group in the hydrocarbon group is substituted by a 2-valent group selected from the group A, or a group represented by the following general formula (II),

R¹¹represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted by a 2-valent group selected from the group A, wherein a plurality of R's are present in the molecule¹¹In the case of (2), they may be the same or different,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰and R¹¹May be a halogen atom substituted for 1 or 2 or more hydrogen atoms in the hydrocarbon groupAtom, cyano, nitro, hydroxy, -OR¹²、-COOR¹²、-CO-R¹²or-SR¹²A substituted group having 1 to 20 carbon atoms,

R¹²represents 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 2-valent group selected from the group A, or a group having 1 to 20 carbon atoms in which 1 or 2 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 a plurality of R's are present in the molecule¹²In the case of (2), they may be the same or different,

group A is-O-, -CO-, -COO-, -NR¹³-、-NR¹³CO-and-S-,

R¹³represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R exist in the molecule¹³In the case of (2), they may be the same or different,

R¹and R²、R²And R³、R³And R⁴、R⁴And R⁵、R⁶And R⁷、R⁷And R⁸、R⁸And R⁹、R⁹And R¹⁰Can be independently linked to each other to form a ring having 3 to 10 carbon atoms consisting of hydrogen atoms and carbon atoms,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹and R¹⁰1 or more of them are groups represented by the following general formula (II),

when a plurality of groups represented by the general formula (II) are present in the molecule, they may be the same group or different groups,

in the general formula (II), R²⁰Represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon groupA group having 1 to 20 carbon atoms which is substituted with a 2-valent group selected from the group B,

X¹represents-NR²¹R²²Or a group represented by the following general formula (a) or the following general formula (b),

R²¹and R²²Each independently represents 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 the hydrocarbon group is substituted by a 2-valent group selected from the following group B,

R²⁰、R²¹and R²²May be a halogen atom, cyano group, nitro group, hydroxy group, -OR²³、-COOR²³、-CO-R²³or-SR²³A substituted group having 1 to 20 carbon atoms,

R²³represents 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 2-valent group selected from the group B, or a group having 1 to 20 carbon atoms in which 1 or 2 or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, wherein a plurality of R's are present in the group²³In the case of (2), they may be the same or different,

group B is-O-, -CO-, -COO-, -NR²⁴-、-NR²⁴CO-and-S-,

R²⁴represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein a plurality of R are present²⁴They may be the same or different,

R²¹and R²²Can be linked to each other to form a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, nitrogen atoms and carbon atoms, or a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms,

n represents a number of 0 or 1,

the x denotes a bonding end of the substrate,

in the general formula (a) and the general formula (b), R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷、R³⁸、R³⁹And R⁴⁰Each independently represents 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 the hydrocarbon group is substituted by a 2-valent group selected from the group C,

R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷、R³⁸、R³⁹and R⁴⁰May be a halogen atom, cyano group, nitro group, hydroxy group, -OR⁴¹、-COOR⁴¹、-CO-R⁴¹or-SR⁴¹A substituted group having 1 to 20 carbon atoms,

R⁴¹represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein a plurality of R exist in the group⁴¹In the case of (2), they may be the same or different,

group C is-O-, -CO-, -COO-, -NR⁴²-、-NR⁴²CO-and-S-,

R⁴²represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein a plurality of R exist in the group⁴²In the case of (2), they may be the same or different,

R³¹and R³²、R³³And R³⁴、R³⁵And R³⁶、R³⁷And R³⁸And R³⁹And R⁴⁰Can be independently linked to each other to form a ring having 2 to 10 carbon atoms consisting of hydrogen atom, nitrogen atom and carbon atom, or a ring having 2 to 10 carbon atoms consisting of hydrogen atom, oxygen atom, nitrogen atom and carbon atom,

denotes a bonding end.

2. The carbamoyloxime compound according to claim 1, wherein R in the general formula (I)⁸Is a group represented by the general formula (II).

3. The carbamoyloxime compound according to claim 2, wherein R in the general formula (I)¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁹And R¹⁰Any 1 or more of them is-CO-R¹¹。

4. The carbamoyloxime compound according to claim 2, wherein R in the general formula (I)¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁹And R¹⁰Any 1 or more of them are nitro groups.

5. The carbamoyloxime compound according to claim 1, wherein R in the general formula (I)³And R⁸Is a group represented by the general formula (II).

6. The carbamoyloxime compound according to any one of claim 1 to 5, wherein,

x in the general formula (II)¹is-NR²¹R²²，

R²¹And R²²And are 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.

7. The carbamoyloxime compound according to any one of claims 1 to 5, wherein,

x in the general formula (II)¹is-NR²¹R²²，

R²¹Is a hydrogen atom, R²²Is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or R²¹And R²²All are aliphatic hydrocarbon groups with 1-20 carbon atoms.

8. A latent alkali-producing agent comprising the carbamoyloxime compound according to any one of claims 1 to 7.

9. A polymerization initiator comprising the carbamoyloxime compound as defined in any 1 of claims 1 to 7.

10. A polymerizable composition comprising the carbamoyloxime compound according to any one of claims 1 to 7, and a polymerizable compound.

11. The polymerizable composition according to claim 10, wherein the polymerizable compound is an epoxy resin or an ethylenically unsaturated compound, or a mixture comprising an epoxy resin and a phenol resin, a mixture comprising an epoxy resin and a thiol compound, or a mixture comprising an ethylenically unsaturated compound and a thiol compound.

12. A cured product of the polymerizable composition according to claim 10 or 11.

13. A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to claim 10 or 11 with an energy ray.

Technical Field

The present invention relates to carbamoyloxime compounds.

Background

Generally, a polymerizable composition such as a photosensitive resin composition is a composition obtained by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and is used for a photocurable ink, a photosensitive printing plate, various photoresists, a photocurable adhesive, and the like because it can be polymerized, cured, or developed by irradiation with energy rays (light).

Photopolymerization initiators are classified into photo radical generators, photo acid generators, and photo base generators according to the active species generated by irradiation with energy rays (light). The photo radical generator has the advantages of high curing speed, no residual active species after curing and the like, and has the following disadvantages: since the inhibition of curing by oxygen occurs, it is necessary to provide a layer that blocks oxygen during curing of the thin film. The photoacid generator has an advantage of not being inhibited by oxygen, and has disadvantages of corroding a metal substrate or modifying a resin after curing due to an acid of a residual active species. The photobase generators are concerned because they are less likely to cause the above-mentioned problems of inhibition of curing by oxygen and corrosion by residual active species, but generally have a problem of low sensitivity (low curability) as compared with the photoacid generators. Photobase generators are described in patent documents 1 and 2, for example.

Documents of the prior art

Patent document

Patent document 1: US9594302

Patent document 2: japanese patent laid-open publication No. 2013-163670

Disclosure of Invention

However, conventional photobase generators have low efficiency of generating alkali and insufficient sensitivity.

Accordingly, an object of the present invention is to provide a compound having high photobase generation efficiency.

The present inventors have conducted intensive studies 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 carbamoyloxime compound represented by the following general formula (I).

[ chemical Structure 1]

(in the formula, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR¹¹、-COOR¹¹、-CO-R¹¹、-SR¹¹A C1-20 hydrocarbon group, a C2-20 heterocycle-containing group, and a methylene group in the hydrocarbon group is selected from<Group A>A group having 1 to 20 carbon atoms substituted with the group having 2 valences in (A)A group or a group represented by the following general formula (II),

R¹¹represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a methylene group in the hydrocarbon group is selected from the group consisting of<Group A>Wherein the group having 1 to 20 carbon atoms is substituted with a group having 2 valences in (A) and a plurality of R's are present in the molecule¹¹In the case of (2), they may be the same or different,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰and R¹¹May be a halogen atom, cyano group, nitro group, hydroxy group, -OR¹²、-COOR¹²、-CO-R¹²or-SR¹²A substituted group having 1 to 20 carbon atoms,

R¹²a hydrocarbon group having 1 to 20 carbon atoms, a methylene group in the hydrocarbon group being selected from<Group A>Wherein the group has 1 to 20 carbon atoms and is substituted with a group having a valence of 2, or a group having 1 to 20 carbon atoms and is substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group for 1 or 2 or more hydrogen atoms in a hydrocarbon group, wherein a plurality of R's are present in the molecule¹²In the case of (2), they may be the same or different,

<group A>is-O-, -CO-, -COO-, -NR¹³-、-NR¹³CO-and-S-,

R¹³represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R exist in the molecule¹³In the case of (2), they may be the same or different,

R¹and R²、R²And R³、R³And R⁴、R⁴And R⁵、R⁶And R⁷、R⁷And R⁸、R⁸And R⁹、R⁹And R¹⁰Can be independently linked to each other to form a ring having 3 to 10 carbon atoms consisting of hydrogen atoms and carbon atoms,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹and R¹⁰Wherein 1 or more of the groups are represented by the following general formula (II),

when a plurality of groups represented by the general formula (II) are present in the molecule, they may be the same group or different groups. )

[ chemical Structure 2]

(in the formula, R²⁰Represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is selected from<Group B>A group having 1 to 20 carbon atoms substituted with the 2-valent group in (A),

X¹represents-NR²¹R²²Or a group represented by the following general formula (a) or the following general formula (b),

R²¹and R²²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is selected from<Group B>A group having 1 to 20 carbon atoms substituted with the 2-valent group in (A),

R²⁰、R²¹and R²²May be a halogen atom, cyano group, nitro group, hydroxy group, -OR²³、-COOR²³、-CO-R²³or-SR²³A substituted group having 1 to 20 carbon atoms,

R²³a hydrocarbon group having 1 to 20 carbon atoms, a methylene group in the hydrocarbon group being selected from<Group B>A group having 1 to 20 carbon atoms substituted with the 2-valent group in (A), or a group having 1 to 20 carbon atoms in which 1 or 2 or more hydrogen atoms in a hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, wherein a plurality of R's are present in the group²³In the case of (2), they may be the same or different,

<group B>is-O-, -CO-, -COO-, -NR²⁴-、-NR²⁴CO-and-S-,

R²⁴represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein a plurality of R are present²⁴They may be the same or different,

R²¹and R²²Can be linked to each other to form a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, nitrogen atoms and carbon atoms, or a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms,

n represents a number of 0 or 1,

denotes a bonding end. )

[ chemical structural formula 3]

(in the formula, R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷、R³⁸、R³⁹And R⁴⁰Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is selected from<Group C>A group having 1 to 20 carbon atoms substituted with the 2-valent group in (A),

R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷、R³⁸、R³⁹and R⁴⁰May be a halogen atom, cyano group, nitro group, hydroxy group, -OR⁴¹、-COOR⁴¹、-CO-R⁴¹or-SR⁴¹A substituted group having 1 to 20 carbon atoms,

R⁴¹represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein a plurality of R exist in the group⁴¹In the case of (2), they may be the same or different,

<group C>is-O-, -CO-, -COO-, -NR⁴²-、-NR⁴²CO-and-S-,

R⁴²represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and is present in the groupPlural R⁴²In the case of (2), they may be the same or different,

R³¹and R³²、R³³And R³⁴、R³⁵And R³⁶、R³⁷And R³⁸And R³⁹And R⁴⁰Can be independently linked to each other to form a ring having 2 to 10 carbon atoms consisting of hydrogen atom, nitrogen atom and carbon atom, or a ring having 2 to 10 carbon atoms consisting of hydrogen atom, oxygen atom, nitrogen atom and carbon atom,

denotes a bonding end. )

Detailed Description

The present invention will be described in detail below.

The carbamoyloxime compound of the present invention is a compound represented by the above general formula (I). The carbamoyloxime compounds represented by the above general formula (I) have geometrical isomers of oxime-based double bonds, but they are not distinguished.

That is, in the present specification, the carbamoyloxime compound represented by the general formula (I) and the compounds and exemplified compounds described later as preferable embodiments of the compound represent a mixture of isomers or any one thereof, and are not limited to the isomers having the structures shown.

Hereinafter, the carbamoyloxime compound represented by the above general formula (I) is also simply referred to as "the compound represented by the general formula (I)" or "the compound of the present invention".

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

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

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and cycloalkylalkyl groups such as cyclohexylmethyl groups, and unsaturated aliphatic hydrocarbon groups having a structure in which a carbon-carbon single bond in these groups is replaced by 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.

As R¹～R¹¹1 OR 2 OR more hydrogen atoms in the hydrocarbon group are replaced by halogen atom, cyano group, nitro group, hydroxy group, -OR¹²、-COOR¹²、-CO-R¹²or-SR¹²Examples of the substituted group having 1 to 20 carbon atoms include a group in which 1 OR 2 OR more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are replaced with a halogen atom, cyano group, nitro group, hydroxyl group, -OR¹²、-COOR¹²、-CO-R¹²or-SR¹²A substituted structure, and the whole group has 1 to 20 carbon atoms. In addition, as R¹²Examples of the group having 1 to 20 carbon atoms in which 1 or 2 or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group include groups having 1 to 20 carbon atoms in which 1 or 2 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, or a hydroxyl group, and the whole group has 1 to 20 carbon atoms.

As R¹～R¹²The methylene group in the hydrocarbon group is selected from the group consisting of<Group A>The C1-20 group substituted with the C2-valent group includes C1-20 hydrocarbon group in which 1 or 2 or more methylene groups are replaced with-O-, -CO-, -COO-, -NR¹³-、-NR¹³A CO-or-S-substituted structure, and the total number of carbon atoms is 1 to 20.

As R²⁰～R²²1 or 2 or more hydrogen atoms in the hydrocarbon group shown areHalogen atom, cyano group, nitro group, hydroxy group, -OR²³、-COOR²³、-CO-R²³or-SR²³Examples of the substituted group having 1 to 20 carbon atoms include a group in which 1 OR 2 OR more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are replaced with a halogen atom, cyano group, nitro group, hydroxyl group, -OR²³、-COOR²³、-CO-R²³or-SR²³A substituted structure, and the whole group has 1 to 20 carbon atoms. In addition, as R²³Examples of the group having 1 to 20 carbon atoms in which 1 or 2 or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group include groups having 1 to 20 carbon atoms in which 1 or 2 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, or a hydroxyl group, and the whole group has 1 to 20 carbon atoms.

As R²⁰～R²³The methylene group in the hydrocarbon group is selected from the group consisting of<Group B>The C1-20 group substituted with the C2-valent group includes C1-20 hydrocarbon group in which 1 or 2 or more methylene groups are replaced with-O-, -CO-, -COO-, -NR²⁴-、-NR²⁴A CO-or-S-substituted structure, and the total number of carbon atoms is 1 to 20.

As R³¹～R⁴⁰1 OR 2 OR more hydrogen atoms in the hydrocarbon group are replaced by halogen atom, cyano group, nitro group, hydroxy group, -OR⁴¹、-COOR⁴¹、-CO-R⁴¹or-SR⁴¹Examples of the substituted group having 1 to 20 carbon atoms include a group in which 1 OR 2 OR more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are replaced with a halogen atom, cyano group, nitro group, hydroxyl group, -OR⁴¹、-COOR⁴¹、-CO-R⁴¹or-SR⁴¹A substituted structure, and the whole group has 1 to 20 carbon atoms.

As R³¹～R⁴⁰The methylene group in the hydrocarbon group is selected from the group consisting of<Group C>The C1-20 group substituted with the 2-valent group in (1) to (20) includes 1 or 2 or more of the above-mentioned C1-20 hydrocarbon groupsMethyl is replaced by-O-, -CO-, -COO-, -NR⁴²-、-NR⁴²A CO-or-S-substituted structure, and the total number of carbon atoms is 1 to 20.

Examples of the heterocycle-containing group having 2 to 20 carbon atoms in the general formula (I) include groups containing a tetrahydrofuryl group, a dioxolanyl group, a tetrahydropyranyl group, a morpholinyl group, a furyl group, a thienyl group, a methylthiophenyl group, a hexylthienyl group, a benzothienyl group, a pyrrolyl group, a pyrrolidinyl group, an imidazolyl group, an imidazolinyl group, an imidazolidinyl group, a pyrazolinyl group, a pyrazolidinyl group, a piperidyl group, and a piperazinyl group.

The heterocycle-containing group having 2 to 20 carbon atoms may have a halogen atom, a cyano group, a nitro group, a hydroxyl group OR⁵⁰、-COOR⁵⁰、-CO-R⁵⁰or-SR⁵⁰The substituents may also contain-O-, -CO-, -COO-, -NR⁵¹-、-NR⁵¹CO-or-S-, etc.

Here, R⁵⁰And R⁵¹Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R⁵⁰And R⁵¹The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms in the general formula (I), the general formula (II), the general formula (a) and the general formula (b).

As R in the above general formula (I)¹And R²、R²And R³、R³And R⁴、R⁴And R⁵、R⁶And R⁷、R⁷And R⁸、R⁸And R⁹、R⁹And R¹⁰The ring having 3 to 10 carbon atoms, which is formed by the mutual connection of hydrogen atoms and carbon atoms, includes a benzene ring, a cyclohexene ring, a cyclohexane ring, a cyclopentadiene ring, a cyclopentane ring, and the like. These rings may have a substituent, and examples of the substituent in this case include substituents which the above-mentioned heterocycle-containing group having 2 to 20 carbon atoms may have.

R in the general formula (II), the general formula (a) and the general formula (b)²¹And R²²、R³¹And R³²、R³³And R³⁴、R³⁵And R³⁶、R³⁷And R³⁸And R³⁹And R⁴⁰The ring having 2 to 10 carbon atoms, which is formed by hydrogen atoms, nitrogen atoms and carbon atoms, being linked to each other, and examples of the ring containing a 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 examples of the substituent in this case include substituents which the above-mentioned heterocycle-containing group having 2 to 20 carbon atoms may have.

R in the general formula (II), the general formula (a) and the general formula (b)²¹And R²²、R³¹And R³²、R³³And R³⁴、R³⁵And R³⁶、R³⁷And R³⁸And R³⁹And R⁴⁰And (b) a ring having 2 to 10 carbon atoms, which is formed by connecting the carbon atoms to each other and is composed of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom, and examples of the ring containing a 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 substituents which the above-mentioned heterocycle-containing group having 2 to 20 carbon atoms may have.

In the present invention, R in the general formula (I) is preferably R in the general formula (I) from the viewpoints of easy synthesis, high storage stability and high alkali-producing efficiency³And R⁸Wherein one or both of them are a group represented by the general formula (II).

R in the general formula (I)¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰Wherein 1 or more other than the group represented by the above general formula (II) is-CO-R¹¹The carbamoyloxime compound (b) is preferred because the resultant polymerizable composition is cured with a low exposure amount. In particular, R⁸Is a group represented by the general formula (II), R³is-CO-R¹¹The carbamoyloxime compound (b) is preferred because it can be easily synthesized and has high storage stability. At this time, R¹¹In the case of an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, the resulting polymerizable composition is preferably cured with a low exposure amount, and therefore, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic group having 2 to 10 carbon atoms is more preferable. Particular preference is given to R¹¹Is phenyl, tolyl, trimethylphenyl, benzofuranyl or thienyl.

In addition, R in the general formula (I)¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰The carbamoyloxime compound having 1 or more nitro groups in (1) other than the group represented by the above general formula (II) is also preferable because the resultant polymerizable composition is cured with a low exposure amount. Particular preference is given to R⁸Is a group represented by the general formula (II), R³Carbamoyloxime compounds which are nitro groups.

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰Each independently being a hydrogen atom, -CO-R¹¹The nitro group or the carbamoyloxime compound of the general formula (II) is preferable because of high alkali-generating efficiency.

Further, X in the general formula (II)¹is-NR²¹R²²The carbamoyloxime compound of (1) is preferable because of its high efficiency of producing a base, and R is more preferable²¹And R²²Are linked to each other to form a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, nitrogen atoms and carbon atoms or a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms.

Particular preference is given to R²¹And R²²Are linked to each other to form a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, and more preferably form a piperidine ring or a pyrrolidine ring.

Further, X in the general formula (II)¹is-NR²¹R²²In the carbamoyloxime compound of (1), R²¹Is a hydrogen atom, R²²The case where the aromatic hydrocarbon group has 6 to 20 carbon atomsAnd R²¹And R²²The aliphatic hydrocarbon group having 1 to 20 carbon atoms is also preferable because of high alkali-generating efficiency.

The carbamoyloxime compound of the general formula (II) wherein n is 0 is preferable because it is highly stable to heat.

The carbamoyloxime compound having n of 1 in the general formula (II) is preferable because the resultant polymerizable composition is cured with a low exposure amount.

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

[ chemical structural formula 4]

[ chemical structural formula 5]

[ chemical structural formula 6]

[ chemical structural formula 7]

[ chemical structural formula 8]

[ chemical structural formula 9]

[ chemical structural formula 10]

[ chemical structural formula 11]

[ chemical structural formula 12]

The method for producing the carbamoyloxime compound of the present invention represented by the above general formula (I) is not particularly limited, and examples thereof include R in the general formula (I)⁸Is a group shown in a general formula (II), X¹is-NR²¹R²²When n is 0, the compound can be produced by the following method according to the following reaction formula 1.

That is, an oxime compound is obtained by reacting a known ketone compound with hydroxylamine hydrochloride in the presence of a base such as pyridine. Subsequently, 4-nitrophenylchloroformate is reacted with an oxime compound, followed by reacting an amine, thereby obtaining the carbamoyloxime compound of the present invention.

[ chemical structural formula 13]

Reaction scheme 1

(in the formula, R¹～R¹⁰、R²⁰～R²²The same as the above general formula (I). )

The above reaction formula 1 represents X¹is-NR²¹R²²In the case of (1), X can be produced by changing the amine used¹Is the above mentioned tubeA compound having a group represented by the formula (a) or the general formula (b).

In addition, the above reaction formula 1 represents R in the general formula (I)⁸In the case of a group of the formula (II), it is also possible to use a group of the formula⁸A ketone compound having a ketone group introduced into an arbitrary position other than the above is used as a raw material to obtain R⁸A compound having a group represented by the general formula (II) introduced into a position other than the above-mentioned positions.

The oxime compound can also be produced by the method described in Japanese patent No. 4223071.

The carbamoyloxime compound of the present invention is useful as a latent alkali-generating agent and a polymerization initiator because it efficiently generates a base and a radical by irradiation with light such as ultraviolet rays or heating, and is particularly useful as a latent alkali-generating agent.

The latent alkali-producing agent of the present invention is a composition containing a compound having a function of efficiently producing an alkali by irradiation with light such as ultraviolet rays, and its use includes a pH adjuster, a catalyst using an alkali, and the like.

In addition, the carbamoyloxime compound of the present invention is useful as a photobase generator and a photoradical polymerization initiator because of high generation efficiency of a base and a radical generated by light irradiation among the above polymerization initiators, and is particularly useful as a photobase generator because of very high base generation efficiency.

The polymerization initiator of the present invention contains at least 1 carbamoyloxime compound represented by the above general formula (I). The polymerization initiator which can be used in combination with the carbamoyloxime compound represented by the above general formula (I) is not particularly limited, and conventionally known photobase generators and photoradical polymerization initiators can be mentioned.

The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass, from the viewpoint of curing the resultant polymerizable composition with a low exposure amount.

The polymerizable composition of the present invention comprises: a polymerization initiator (A) containing at least 1 carbamoyloxime compound represented by the 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), from the viewpoint of curing the resultant polymerizable composition with a low exposure amount. The content of the polymerization initiator (a) is preferably not more than 1 part by mass because curing defects due to insufficient curing sensitivity can be easily prevented, and therefore, it is preferably not more than 20 parts by mass because volatiles during light irradiation or heating can be suppressed.

The polymerizable compound (B) used in the present invention includes a compound having an anionic polymerizable functional group, a compound which is cured by a reaction in which a base acts as a catalyst or a reaction in which a base is added, and a radical polymerizable compound, and a photosensitive resin which is cured by polymerization by irradiation with an energy ray such as ultraviolet light or a cured resin whose curing temperature is lowered is preferable because the resultant polymerizable composition is cured with a low exposure amount. The anionic polymerizable functional group is a functional group capable of being polymerized by a base generated from a photobase generator by an active energy ray such as ultraviolet rays, and examples thereof include an epoxy group, an episulfide group, a cyclic monomer (σ -valerolactone, ∈ -caprolactam), and a malonate. Examples of the reaction in which a base acts as a catalyst or the reaction in which a base is added include a urethane bond formation reaction by an isocyanate and an alcohol, an addition reaction of an epoxy resin and a hydroxyl group-containing compound, an addition reaction of an epoxy resin and a carboxylic acid group-containing compound, an addition reaction of an epoxy resin and a thiol compound, a michael addition reaction of a (meth) acryloyl group, a dehydration condensation reaction of a polyamic acid, and a hydrolysis/polycondensation reaction of an alkoxysilane.

Examples of the compound having an anionic polymerizable functional group include epoxy resins, oxetane resins, episulfide resins, cyclic amides (lactam-based compounds), cyclic esters (lactone-based compounds), cyclic carbonate-based compounds, and malonic acid esters. Examples of the compound that is cured by a reaction in which a base acts as a catalyst or a reaction in which a base is added include polyamide resins (polyimidization reaction by dehydrative cyclization), epoxy-hydroxy 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 (cross-linking copolymerization), oxetane-hydroxy 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), episulfide-hydroxy systems (ring-opening addition reaction), episulfide-carboxylic acid systems (ring-opening addition reaction), Episulfide thiol series (ring-opening addition reaction), episulfide anhydride series (ring-opening polycondensation), acrylic acid thiol series (michael addition reaction), methacrylic acid thiol series (michael addition reaction), acrylic acid amine series (michael addition reaction), methacrylic acid amine series (michael addition reaction), carboxylic acid hydroxyl series (polyesterification reaction), carboxylic acid amine series (polyamidation reaction), isocyanate hydroxyl series (urethanization reaction), isocyanate thiol series (polythiourethanization reaction), alkoxysilane series (hydrolysis polycondensation), and the like. Examples of the compound that is polymerized by a radical include ethylenically unsaturated compounds. From the viewpoint of high reactivity, a compound which undergoes radical polymerization is preferably used. These resins may be used alone, or 2 or more of them may be used in combination. A preferable combination is a combination of an epoxy resin and a phenol resin in terms of rapid reaction and good adhesiveness, a combination of an epoxy resin and a thiol compound in terms of excellent low-temperature curability, and a combination of an ethylenically unsaturated compound and a thiol compound in terms of high reactivity.

The epoxy resin may have an epoxy group, but does not include the carbamoyloxime compound of the present invention. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, catechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (o-cresol), ethylenebisphenol, isopropylidenebisphenol (bisphenol A), 4' -dihydroxybenzophenone, isopropylidenebis (o-cresol), tetrabromobisphenol A, 1, 3-bis (4-hydroxycumylbenzene), 1, 4-bis (4-hydroxycumylbenzene), 1, 3-tris (4-hydroxyphenyl) butane, polyglycidyl ether compounds of polynuclear polyphenol compounds such as 1, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxobisphenol, phenol novolac, o-cresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenol; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyalkylene glycol, thiodiethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol a-ethylene oxide adducts; 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; epoxy compounds having a glycidylamino group such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidylanthro-toluidine and the like; epoxides of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, 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 resins obtained by internally crosslinking a prepolymer of a terminal isocyanate or resins obtained by polymerizing a polyvalent active hydrogen compound (e.g., a polyphenol, a polyamine, a carbonyl group-containing compound, or a polyphosphate) to a high molecular weight.

Among the above epoxy resins, epoxy resins having a glycidyl group are preferable, and epoxy resins having a glycidyl group of 2 or more functions are more preferable, from the viewpoint of excellent curability of the resultant polymerizable composition.

The phenol resin may have a phenolic hydroxyl group, but the carbamoyloxime compound and the epoxy resin are not included. The phenol resin is preferably a phenol resin having 2 or more hydroxyl groups in 1 molecule, and a conventionally known phenol resin can be used, because the obtained polymerizable composition has excellent curability. Examples of the phenol resin include bisphenol a type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol a novolac type phenol resin, glycidyl ester type phenol resin, aralkyl type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton-modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic type phenol resin, polyhydric alcohol type phenol resin, phosphorus-containing phenol resin, phenol resin containing a polymerizable unsaturated hydrocarbon group, and silicone resins containing a hydroxyl group, there is no particular limitation. These phenol resin can be used alone in 1 or a combination of 2 or more.

The thiol compound may have a thiol group, but the carbamoyloxime compound, the epoxy resin, and the phenol resin are not included. Among the thiol compounds, compounds having 2 or more thiol groups in 1 molecule are preferable in terms of excellent curability of the resultant polymerizable composition.

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-thietane, and the like, Pentaerythritol tetrathiol, 1, 3, 3-tetrakis (mercaptomethylthio) propane, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, and trimethylolpropane trimercaptopropionate, and more preferably 1, 2, 6, 7-tetramercapto-4-thiaheptane, pentaerythritol tetrathiol, 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 tetramercaptopropionate, and pentaerythritol tetramercaptoacetate.

Particularly preferred compounds are 1, 2, 6, 7-tetramercapto-4-thiaheptane, pentanetetrathiol, bis (2-mercaptoethyl) sulfide, 2, 5-dimercaptomethyl-1, 4-dithiane, and 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane.

The thiol compound may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the polyamide resin include those obtained from an acid dianhydride selected from ethylene tetracarboxylic dianhydride, 1, 2, 3, 4-benzenetetracarboxylic dianhydride, 1, 2, 3, 4-cyclohexanetetracarboxylic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2, 3, 3-biphenyltetracarboxylic dianhydride, 1, 4, 5, 8-naphthalenetetracarboxylic dianhydride and a diamine selected from (o-, m-or p-phenylenediamine), (3, 3 '-or 4, 4') -diaminodiphenyl ether, diaminobenzophenone, (3, 3 '-or 4, 4') -diaminodiphenylmethane.

Examples of the polyurethane resin include resins obtained from a polyfunctional isocyanate such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate and a polyol (polyfunctional alcohol) such as polyether polyol, polyester polyol, or polycarbonate polyol.

Examples of the nylon resin include resins produced from cyclic monomers such as epsilon-caprolactam and laurolactam.

Examples of the polyester resin include resins obtained from cyclic monomers such as δ -valerolactone and β -propiolactone.

The ethylenically unsaturated compound may have an ethylenically unsaturated bond, but the carbamoyloxime compound, the epoxy resin, the phenol resin, and the thiol compound are not included. Examples of the ethylenically unsaturated compound include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene fluoride, and tetrafluoroethylene; mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as (meth) acrylic acid, α -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ester ], phthalic acid mono [2- (meth) acryloyloxyethyl ester ], and ω -carboxy polycaprolactone mono (meth) acrylate; unsaturated polybasic acids such as (meth) acrylic acid/hydroxyethyl maleate, (meth) acrylic acid/hydroxypropyl maleate, dicyclopentadiene/maleate, or polyfunctional (meth) acrylates having 1 carboxyl group and 2 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 (meth) 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, poly (ethoxy) ethyl (meth) acrylate, poly (ethoxy) acrylate, poly (meth) acrylate, poly (iso-butyl (meth) acrylate, poly (iso-hexyl (meth) acrylate, poly (iso-2-octyl (meth) acrylate, poly (iso-butyl acrylate, poly (meth) acrylate, poly (iso-2-butyl acrylate, poly (meth) acrylate, poly (iso-2, Butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (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, propylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, propylene glycol (meth) acrylate, propylene glycol (acrylate, ethylene glycol (acrylate, propylene glycol (meth) acrylate, and pentaerythritol tetra (meth) acrylate, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tris [ (meth) acryloylethyl ] isocyanurate, and polyester (meth) acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; anhydrides 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 adducts, dodecenylsuccinic anhydride, and methylnadic anhydride; amides of unsaturated monobasic acids and polyamines such as (meth) acrylamide, methylenebis (meth) acrylamide, diethylenetriamine tri (meth) acrylamide, xylylenebis (meth) acrylamide, α -chloroacrylamide, and N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as acryloyl; unsaturated nitriles such as (meth) acrylonitrile, α -chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzylmethyl ether, and vinylbenzylglycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; macromonomers having a mono (meth) acryloyl group at the terminal of the molecular chain of a polymer such as polystyrene, poly (methyl (meth) acrylate), poly (n-butyl (meth) acrylate), or 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, vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxides.

The ethylenically unsaturated compounds may be used alone or in combination of 2 or more.

As the above-mentioned ethylenically unsaturated compound, commercially available products can be used, and examples thereof include: KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (manufactured by Nippon Chemicals, supra); ARONIX M-215, M-350 (above, made by Toyo Synthesis); NK ESTER A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (manufactured by Xinzhongcun chemical industry); SPC-1000, SPC-3000 (above, Zhao Shu and electrician), etc.

The content of the polymerizable composition (B) may be an amount suitable for the purpose of use, and in order to prevent curing failure, the content is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more, of the solid components (all components except the solvent) in the polymerizable composition.

In the polymerizable composition of the present invention, additives such as an inorganic compound, a coloring material, a latent epoxy curing agent, a chain transfer agent, a sensitizer, and a solvent can be used as optional components.

Examples of the inorganic compound 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 powder), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, and the like. These inorganic compounds are used as, for example, fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

Examples of the coloring material include pigments, dyes, natural pigments, and the like. These colorants may be used alone or in combination of 2 or more.

As the above-mentioned pigment, for example, a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; a phthalocyanine compound; isoindolinone compounds; isoindoline compounds; a quinacridone compound; an anthanthrone compound; a perinone compound; a perylene compound; diketopyrrolopyrrole compounds; a thioindigo compound; a dioxazine compound; a triphenylmethane compound; a quinophthalone compound; naphthalene tetracarboxylic acid; metal complex compounds of azo dyes, cyanine dyes; a lake pigment; carbon black obtained by a furnace method, a tank method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black; a carbon black prepared by adjusting or coating the carbon black with an epoxy resin, a carbon black prepared by dispersing the carbon black with a resin in a solvent in advance and adsorbing 20 to 200mg/g of the resin, a carbon black prepared by subjecting the carbon black to an acidic or basic surface treatment, a carbon black having an average particle diameter of 8nm or more and a DBP oil absorption of 90ml/100g or less, a carbon black prepared by converting CO and CO contained in volatile components at 950 ℃, a carbon black prepared by converting a carbon black into a volatile component, and a method for producing the same₂The calculated total oxygen amount is per 100m²Carbon black of 9mg or more; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; nigrosine, pigment black 7, titanium black;organic or inorganic pigments such as chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, ultramarine, prussian blue, ultramarine, viridian (viridian), emerald green, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination of two or more.

As the pigment, commercially available pigments can be used, and examples thereof include 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, 184, 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, 114, 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 dye include azo dyes, anthraquinone dyes, indigo 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 a plurality of these dyes may be used in combination.

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

As the chain transfer agent or sensitizer, a compound containing a sulfur atom is generally used. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptobutanoic 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, thiosalicylic acid, 2-mercaptopropionic acid, and the like, Mercapto compounds such as 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, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, iodinated alkyl compounds such as 3-iodopropanesulfonic acid, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioacetate, ethylene glycol bisthioglycolate, Trimethylolpropane trimercaptoacetate, butanediol bisthiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetramercaptoacetate, trimethylolethyltrithiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following aliphatic polyfunctional thiol compounds such as compound No. C1 and tris (2-hydroxyethyl) isocyanurate of trimercaptopropionic acid, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko K.K., and the like.

[ chemical structural formula 14]

Compound No. C1

As the solvent, a solvent capable of dissolving or dispersing the above components (the polymerization initiator (a), the polymerizable compound (B), and the like) can be usually used, and for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; lactone solvents such as γ -caprolactone, δ -caprolactone and γ -butyrolactone; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso-or n-propanol, iso-or n-butanol, and pentanol; ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; paraffin solvents such as mineral spirits, Swasol #310(Cosmo Songshan oil Co., Ltd.), Solvesso #100(Exxon chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; a carbitol-based solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; n, N-dimethylformamide; n, N-dimethylacetamide; n-methyl pyrrolidone; dimethyl sulfoxide; water, etc., and 1 or 2 or more kinds of these solvents can be used as a mixed solvent.

Among them, from the viewpoint of alkali developability, pattern formability, film forming property, and solubility, a ketone or ether ester solvent is preferably used, and propylene glycol-1-monomethyl ether-2-acetate (hereinafter, also referred to as "PGMEA") or cyclohexanone is particularly preferably used.

In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, and the components are uniformly dispersed or dissolved, and the polymerizable composition of the present invention may be in a liquid or paste form in an amount suitable for each application, and in order to obtain a uniform cured product, it is generally preferable to contain the solvent in a range where the amount of solid components (all components except the solvent) in the polymerizable composition of the present invention is 10 to 90 mass%.

In addition, the polymerizable composition of the present invention can improve the properties of a cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, a methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, a styrene- (meth) acrylic acid copolymer, a (meth) acrylic acid-methyl methacrylate copolymer, an ethylene-vinyl chloride copolymer, an ethylene-vinyl copolymer, a polyvinyl chloride resin, an ABS resin, nylon 6, nylon 66, nylon 12, a polyurethane resin, polycarbonate polyvinyl butyral, a cellulose ester, polyacrylamide, a saturated polyester, a phenol resin, a phenoxy resin, and the like.

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), from the viewpoint of excellent curability of the resultant polymerizable composition.

The polymerizable composition of the present invention may further contain a surfactant, a silane coupling agent, a melamine compound, and the like in combination.

As the surfactant, a fluorine-based surfactant such as perfluoroalkyl phosphate ester and perfluoroalkyl carboxylate; anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates, and alkyl sulfates; cationic surfactants such as higher amine halides 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; an amphoteric surfactant; surfactants such as silicone surfactants, and the like may be used in combination.

As the silane coupling agent, for example, silane coupling agents 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 and KBE-403 are preferably used.

Examples of the melamine compound include (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolActive hydroxymethyl (CH) in nitrogen compound such as urea₂OH group) or a compound in which all or a part (at least 2) of the OH groups) is etherified with an alkyl group.

Examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same or different from each other. The methylol group not etherified with an alkyl group may be self-condensed in one molecule or may be condensed between two molecules, and as a result, an oligomer component is formed.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, or the like can be used.

Among them, alkyl-etherified melamines such as hexamethoxy methyl melamine and hexabutoxy methyl melamine are preferable from the viewpoint of solubility in a solvent and difficulty in crystallization from the polymerizable composition.

In the polymerizable composition of the present invention, the content of the optional components other than the polymerization initiator (a) and the polymerizable compound (B) (excluding the inorganic compound, the coloring material and the solvent) is appropriately selected depending on the purpose of use thereof, and is not particularly limited, and from the viewpoint of excellent curability of the resultant polymerizable composition, it is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the polymerizable compound (B).

The polymerizable composition of the present invention can be irradiated with an energy ray to produce a cured product. The cured product is formed into an appropriate shape according to the application. For example, in the case of 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, plastic, or the like by a known means such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, or the like. Further, the transfer may be performed once on a support substrate such as a film and then transferred to another support substrate, and the application method is not limited.

As the light source of the energy ray used for curing the polymerizable composition of the present invention, an electromagnetic wave energy having a wavelength of 2000 to 7000 angstroms, an electron ray, an X-ray, a radioactive ray, or other high-energy rays obtained from an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, a germicidal lamp, a light-emitting diode, a CRT light source, or the like can be used, and from the viewpoint of excellent curability of the obtained polymerizable composition, it is preferable to use an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, or the like that emits light having a wavelength of 300 to 450 nm.

Further, the laser direct writing method, which forms an image directly from digital information from a computer or the like without using a mask by using a laser as an exposure light source, is useful because it can improve not only productivity but also resolution, positional accuracy and the like, and as the laser, a light having a wavelength of 340 to 430nm is preferably used. When these lasers are used, it is preferable to add a sensitizing dye that absorbs light in the visible to infrared region from the viewpoint of excellent curability of the resultant polymerizable composition.

In curing the polymerizable composition of the present invention, it is usually necessary to heat the composition after the irradiation with the energy ray, and from the viewpoint of the curing rate, heating at about 40 to 150 ℃ is preferred.

The polymerizable composition of the present invention can be used for photocurable coatings or varnishes; a photocurable adhesive; a coating agent for metal; a printed substrate; color filters in liquid crystal display elements for color displays such as color televisions, PC monitors, portable information terminals, and digital cameras; a color filter of the CCD image sensor; electrode materials for plasma display panels; powder coating; printing ink; printing plates; an adhesive; a dental composition; gel coating; photoresist for electronic engineering; electroplating a corrosion inhibitor; etching the resist; drying the film; a solder resist; resists for forming structures of color filters for various display applications or plasma display panels, electroluminescent display devices, and LCDs in the manufacturing process thereof; a composition for encapsulating electric and electronic components; a solder resist; a magnetic recording material; a micro mechanical component; a waveguide; an optical switch; a mask for plating; etching the mask; a color testing system; a fiberglass cable coating; a stencil for screen printing; a material for producing a three-dimensional object by stereoscopic imaging; a material for holographic recording; an image recording material; a fine electronic circuit; a decolorizing material; a decolorizing material for an image recording material; a decolorization material for image recording materials using microcapsules; a photoresist material for a printed circuit board; photoresist materials for UV and visible laser direct imaging; the application of the photoresist material, the protective film, and the like used for forming the dielectric layer in the successive lamination of the green sheet is not particularly limited.

The polymerizable composition of the present invention can be used for the purpose of forming a spacer for a liquid crystal display panel and for the purpose of forming a protrusion for a vertical alignment type liquid crystal display element. Particularly, the photosensitive resin composition is useful as a photosensitive resin composition for simultaneously forming a protrusion and a spacer for a vertical alignment type liquid crystal display element.

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

The polymerizable composition of the present invention to which a coloring material is added is suitably used as a resist for each pixel such as RGB constituting a color filter and a resist for a black matrix forming a partition wall of each pixel. Further, in the case of a black matrix resist to which an ink repellent is added, it is preferably used for a partition wall for an ink jet color filter having an outline angle of 50 ° or more. As the ink repellent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant are preferably used.

In the case of using the partition wall for the ink-jet color filter, an optical element is manufactured by the following method: the partition wall formed of the polymerizable composition of the present invention partitions the transfer-receiving body, and the ink jet method is used to form the image area by applying the liquid droplets to the recessed portions of the partitioned transfer-receiving body. In this case, the optical element manufactured by the above manufacturing method preferably has at least a pixel group including a plurality of color regions and a partition wall for separating the color regions of the pixel group on a substrate.

The polymerizable composition of the present invention can also be used as a composition for a protective film or an insulating film. In this case, the ultraviolet absorber, the alkylated modified melamine and/or the acrylic modified melamine, the 1 or 2 functional (meth) acrylate monomer having an alcoholic hydroxyl group in the molecule, and/or the silica sol may be contained.

The insulating film is used for the insulating resin layer in a laminate having the insulating resin layer provided on a releasable supporting substrate, the laminate can be developed with an alkaline aqueous solution, and the thickness of the insulating resin layer is preferably 10 to 100 μm.

The polymerizable composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound. The photosensitive paste composition can be used for forming a baked material pattern such as a partition wall pattern, a dielectric pattern, an electrode pattern, a black matrix pattern, and the like of a plasma display panel.

Examples

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 compound obtained below is "liquid" means that it is liquid at 25 ℃ under atmospheric pressure.

EXAMPLE 1 Synthesis of Compound 1

Compound 1 was synthesized according to the scheme shown below.

[ chemical structural formula 15]

(Synthesis of Oxime body 1)

In a 100ml four-necked flask, 2- (4- ((4- (2-methylbenzoyl) phenyl) thiol) phenyl) acetonitrile 1.0eq, sodium hydroxide 1.0eq, dissolved in ethanol (100% by weight of theoretical yield) was added, and stirring was performed at 5 ℃ on an ice bath. To this was added dropwise a solution obtained by dissolving isobutyl nitrite 1.0eq in ethanol (100% by weight of theoretical yield). The reaction solution was returned to room temperature, stirred for 2 hours, filtered, and the filtrate was concentrated. To this was added ethyl acetate, and the mixture was washed with ion-exchanged water 3 times, dried over magnesium sulfate, and concentrated again. The residue was purified by silica gel column chromatography (eluent was ethyl acetate and hexane ═ 1: 5), and the desired compound was obtained as a brown viscous liquid compound in a yield of 60%.

(Synthesis of Compound 1)

In a 100ml four-necked flask, 1.0eq. of oxime 1, methylene chloride (500 wt% of theoretical yield), and triethylamine 2.0eq. were added, and the mixture was stirred at 5 ℃ in an ice bath. A solution obtained by dissolving 4-nitrophenyl chloroformate at 1.1eq in methylene chloride was added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling again to 5 ℃ in an ice bath, 1.1eq of piperidine was added dropwise. After stirring at room temperature for 3 hours, the solvent was distilled off under reduced pressure. Ethyl acetate and a 5 mass% aqueous NaOH solution were added thereto to perform oil-water separation. The organic layer was further washed with ion-exchanged water 3 times, and then concentrated. Ethanol was added to the residue to crystallize it, whereby the objective compound was obtained as a pale yellow powdery compound in a yield of 79%. Performing TG-DTA (melting point) measurement of the obtained compound, and¹H-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.

[ chemical structural formula 16]

(Synthesis of Oxime body 2)

In a 100ml four-necked flask, 1.0eq of 2, 2, 2-trifluoro-1- (4- ((4- (2-methylbenzoyl) phenyl) thio) phenyl) ethan-1-one was added, dissolved in ethanol (600 wt% of theory). 1.2eq of hydroxylammonium chloride and 3.0eq 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 extracted with ethyl acetate. The organic layer was washed with 5 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 was ethyl acetate and hexane ═ 1: 5), and the desired product was obtained as a brown viscous liquid compound in a yield of 76%.

(Synthesis of Compound 2)

The procedure of example 1 was followed except that oxime body 1 was changed to oxime body 2, and the procedure was followed by a water washing step. The concentrated residue was purified by silica gel column chromatography (eluent was ethyl acetate and hexane ═ 1: 5), and the target compound was obtained as a yellow viscous liquid compound in a yield of 76%. By carrying out the resulting compound¹H-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.

[ chemical structural formula 17]

(Synthesis of Compound 3)

In a 100ml four-necked flask, 1.0eq. of oxime 3, methylene chloride (600 wt% of theoretical yield), and 2.8eq. of triethylamine were added, and the mixture was stirred at 0 ℃ in an ice bath. A solution obtained by dissolving 2.1eq of 4-nitrophenyl chloroformate in methylene chloride was added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling again to 0 ℃ in an ice bath, 2.1eq. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed 2 times with a 1 mass% NaOH aqueous solution and 3 times with ion-exchanged water. The organic layer was dried over magnesium sulfate and concentrated, and the residue was subjected to silica gel column chromatography (eluent)Ethyl acetate: hexane ═ 1: 3) and (5) refining the residue. Ethanol (1500% by weight of the theoretical yield) was added thereto to conduct crystallization, and the objective compound was obtained as a pale yellow powdery compound in a yield of 63%. Performing TG-DTA (melting point) measurement of the obtained compound, and¹H-NMR measurement. 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.

[ chemical structural formula 18]

(Synthesis of Oxime body 4)

1- (4- ((4-nitrophenyl) thio) phenyl) dodecane-1-one 1.0 eq.% was added to a 100ml four-necked flask, dissolved in dimethylformamide (300% by weight of theory). To the solution was added 3.2eq of hydroxylammonium chloride and 3.2eq of sodium hydroxide. The reaction mixture was heated and stirred at 65 ℃ for 2 hours, ion-exchanged water was added thereto, and extraction was performed with ethyl acetate. After washing with ion-exchanged water 3 times, 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). Thus, the target compound was obtained as a pale yellow solid in a yield of 61%.

(Synthesis of Compound 4)

In a 100ml four-necked flask, 1.0eq. of oxime 4, methylene chloride (600 wt% of theoretical yield), and 2.0eq. of triethylamine were added, and the mixture was stirred at 0 ℃ in an ice bath. A solution obtained by dissolving 4-nitrophenyl chloroformate at 1.3eq in methylene chloride was added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling again to 0 ℃ in an ice bath, 1.3eq. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed 2 times with a 1 mass% NaOH aqueous solution and 3 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). In this way,the target compound was obtained as a pale brown liquid compound in a yield of 72%. By carrying out the resulting compound¹H-NMR measurement. The results are shown in Table 2.

EXAMPLE 5 Synthesis of Compound 5

Compound 5 was synthesized according to the scheme shown below.

[ chemical structural formula 19]

(Synthesis of Oxime Compound 5)

1- (4- ((4-nitrophenyl) thio) phenyl) dodecane-1-one 1.0eq. was added to a 100ml four-necked flask, dissolved in THF (350% by weight of theory). 4M HCl-ethyl acetate 1.0eq and isobutyl nitrite 1.2eq were added thereto, and the mixture was stirred at 35 ℃ for 3 hours. To the reaction solution was added methyl isobutyl ketone, and the mixture was washed with ion-exchanged water 6 times, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent, ethyl acetate, hexane, 1: 8). Thus, the target compound was obtained as a pale brown liquid compound in a yield of 86%.

(Synthesis of Compound 5)

The procedure of example 1 was followed except that oxime body 1 was changed to oxime body 5, and the procedure was followed by a water washing step. The reaction mixture was concentrated to obtain the desired compound as a brown liquid in a yield of 41%. By carrying out the resulting compound¹H-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.

[ chemical structural formula 20]

(Synthesis of Compound 6)

The same operation as in example 1 was carried out, except that oxime 1 was changed to oxime 5 and piperidine was changed to di-n-butylamineThe process proceeds to the water washing step. The residue was concentrated, and the residue was purified by silica gel column chromatography (eluent, ethyl acetate, hexane, 1: 7). Thus, the target compound was obtained as a pale yellow liquid compound in a yield of 28%. By carrying out the resulting compound¹H-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.

[ chemical structural formula 21]

(Synthesis of Oxime body 6)

1- (4- ((4- (thiophene-2-carbonyl) phenyl) thio) phenyl) ethan-1-one 1.0eq. was added to a 100ml four-necked flask, dissolved in dimethylformamide (400% by weight of theory). 1.1eq of hydroxylammonium chloride and 1.1eq of pyridine are added to the solution. The reaction mixture was heated and stirred at 55 ℃ for 2 hours. Ethyl acetate (400 wt% of theoretical yield) was added to the reaction solution, and ion-exchanged water (800 wt% of theoretical yield) was added dropwise thereto to perform crystallization, thereby obtaining the target compound in 89% yield.

(Synthesis of Compound 7)

In a 100ml four-necked flask, 1.0eq. of oxime 6, methylene chloride (600 wt% of theoretical yield), and 2.0eq. of triethylamine were added, and the mixture was stirred at 0 ℃ in an ice bath. A solution obtained by dissolving 4-nitrophenyl chloroformate at a value of 1.5eq in methylene chloride was added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling again to 0 ℃ in an ice bath, 1.5 eq.of di-n-butylamine were added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed 2 times with a 1 mass% NaOH aqueous solution and 3 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: toluene: 1: 15). Thus, the target compound was obtained as a pale yellow solid in a yield of 59%. TG-DTA (melting point) measurement of the obtained compound was carried outAnd, and¹H-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.

[ chemical structural formula 22]

(Synthesis of Oxime body 7)

In a 100ml four-necked flask was added 1.0 eq.% of 3-cyclohexyl-1- (4- ((4- (2-methylbenzoyl) phenyl) thio) phenyl) propan-1-one, dissolved in dimethylformamide (300% by weight of theory). 1.1eq of hydroxylammonium chloride and 1.1eq of pyridine are added to the solution. The reaction mixture was heated at 60 ℃ with stirring for 3 hours, ion-exchanged water was added thereto, and extraction was performed with ethyl acetate. After washing with ion-exchanged water 3 times, 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). Thus, the target compound was obtained as a pale yellow solid in a yield of 60%.

(Synthesis of Compound 8)

The procedure of example 1 was followed except that oxime body 1 was changed to oxime body 7, and the procedure was followed by a water washing step. The reaction mixture was concentrated to obtain the objective compound as a pale brown liquid compound in a yield of 50%. By carrying out the resulting compound¹H-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 procedure shown below.

[ chemical structural formula 23]

(Synthesis of comparative Compound 1)

The same procedures as in example 7 were repeated except that di-n-butylamine was changed to n-butylamineThe operation of (2) is carried out to the water washing step. The residue was concentrated, and the residue was purified by silica gel column chromatography (eluent, ethyl acetate: toluene: 1: 8). Thus, the target compound was obtained as a pale yellow solid in a yield of 81%. Performing TG-DTA (melting point) measurement of the obtained compound, and¹H-NMR measurement. The results are shown in tables 1 and 2, respectively.

TABLE 1

	Name of Compound	Melting Point (. degree.C.)
			Example 1	Compound 1	152
Example 2	Compound 2	(liquid)
			Example 3	Compound 3	140
Example 4	Compound 4	(liquid)
			Example 5	Compound 5	(liquid)
Example 6	Compound 6	(liquid)
			Example 7	Compound 7	66
Example 8	Compound 8	(liquid)
			Comparative example 1	Comparative Compound 1	95

TABLE 2

Examples 9 and 10 and comparative examples 2 and 3 preparation of polymerizable composition

The compounding described in table 3 was performed to obtain polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2. In the table, the blending numerical values represent parts by mass.

In addition, 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 193g/eq., manufactured by Nippon Chemicals Co., Ltd.)

B-2: H-3M (phenolic resin, hydroxyl equivalent 105 ~ 109g/eq., manufactured by Minghe chemical Co., Ltd.)

C-1: FZ-2122 (polyether-modified polysiloxane, manufactured by Dow Corning Toray Co., Ltd., 1 wt% PGMEA solution)

D-1: cyclopentanone (solvent)

TABLE 3

[ chemical structural formula 24]

Evaluation examples 1 and 2 and comparative evaluation examples 1 and 2

The presence or absence of residual films was confirmed in 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.

The polymerizable compositions 1 and 2 and the comparative polymerizable compositions 1 and 2 (coating amount of about 2mL) were coated on a glass substrate (10cm × 10cm) with a spin coater (500rpm × 2 sec → 1000rpm × 10 sec → tilt × 0.5 sec), and pre-baked in an oven (90 ℃ × 90 sec) to form a film.

Each film was covered with a stepwise exposure table (33-step type, OD value 0-3, table 4) having a continuously changing transmittance, and irradiated with a predetermined amount of ultraviolet light (illuminance 20 mW/cm) using a UV-LED (365nm)²Exposure time 150 seconds, cumulative exposure 3000mJ/cm²)。

After exposure, post-baking (100 ℃ C. times.20 minutes), development (PGMEA, 30 seconds) and rinsing (isopropanol, 10 seconds) were performed in an oven.

The number of remaining stages was visually confirmed for the obtained cured film sample. The number of remaining stages refers to the maximum number of stages in which the cured film remains. The transmittance was determined from the remaining number of steps in table 4, and the conversion sensitivity was calculated by using the following formula.

Conversion sensitivity (mJ/cm)²) Cumulative exposure (3000 mJ/cm)²) X transmittance (%)

The remaining number of stages and the conversion sensitivity are shown in table 5.

TABLE 4

Number of stages	OD value	Transmittance (%)
			0	0	100.000
1	0.06	87.096
			2	0.15	70.795
3	0.24	57.544
			4	0.35	44.668
5	0.44	36.308
			6	0.54	28.840
7	0.64	22.909
			8	0.74	18.197
9	0.84	14.454
			10	0.94	11.482
11	1.05	8.913
			12	1.15	7.079
13	1.25	5.623
			14	1.35	4.467
15	1.44	3.631
			16	1.54	2.884
17	1.64	2.291
			18	1.74	1.820
19	1.84	1.445
			20	1.94	1.148
21	2.04	0.912
			22	2.14	0.724
23	2.24	0.575
			24	2.34	0.457
25	2.44	0.363
			26	2.54	0.288
27	2.65	0.224
			28	2.75	0.178
29	2.84	0.145
			30	2.93	0.117
31	2.95	0.112
			32	2.97	0.107
33	3.00	0.100

TABLE 5

From the results shown in Table 5, it is understood that the polymerizable composition containing the carbamoyloxime compound of the present invention has a higher number of residual steps (higher curability) than the comparative polymerizable composition, and therefore, has a high photobase efficiency, can be cured at a low exposure amount, and has a high sensitivity to a UV-LED light source. Therefore, it was found that the compound of the present invention is excellent as a polymerization initiator.

EXAMPLE 11 Synthesis of Compound 9

Compound 9 was synthesized according to the scheme shown below.

[ chemical structural formula 25]

(Synthesis of Oxime Compound 8)

1, 1' - (thiobis (4, 1-phenylene)) bis (hexane-1-one) 1.0eq was charged in a 100ml four-necked flask and dissolved in dimethylformamide (400% by weight of theory). 2.6eq of hydroxylammonium chloride and 2.6eq of pyridine are added to the solution. After the reaction mixture was heated and stirred at 55 ℃ for 7 hours, ion-exchanged water was added thereto, and the mixture was extracted with ethyl acetate. The organic layer was washed with ion-exchanged water 3 times, dried over magnesium sulfate, and concentrated. 1, 2-dichloroethane (12000 wt% of theoretical yield) was added thereto and recrystallized to obtain the desired product as a white powder in a yield of 77%.

(Synthesis of Compound 9)

In a 100ml four-necked flask, 1.0eq. of oxime 8, dichloroethane (600% by weight of theoretical yield), and 4.0eq. of triethylamine were added, and the mixture was stirred at 5 ℃ in an ice bath. To this was added dropwise a solution obtained by dissolving 3.0eq. of 4-nitrophenyl chloroformate in dichloroethane (300% by weight of theoretical yield). After the completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling again to 5 ℃ in an ice bath, 3.0eq of aniline was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto to conduct oil-water separation. The organic layer was washed with 1 mass% aqueous sodium hydroxide solution 3 times, ion-exchanged water 2 times, and magnesium sulfateDrying and concentrating. The residue was purified by silica gel column chromatography (eluent, ethyl acetate: toluene: 1: 25), and the desired product was obtained as a white powdery compound in a yield of 57%. Performing TG-DTA (melting point) measurement of the obtained compound, and¹H-NMR measurement. 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.

[ chemical structural formula 26]

(Synthesis of Compound 10)

The procedure of example 11 was repeated except that the aniline was changed to 4-methylpiperidine, and the washing step was carried out. The concentrated residue was purified by silica gel column chromatography (eluent, ethyl acetate: toluene ═ 1: 5), and the desired product was obtained as a pale yellow viscous liquid compound in a yield of 80%. By carrying out the resulting compound¹H-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.

[ chemical structural formula 27]

(Synthesis of Oxime Compound 9)

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

(Synthesis of Compound 11)

The procedure of example 11 was followed to carry out the water washing step, except that oxime body 1 was changed to oxime body 9 and aniline was changed to dibutylamine. The concentrated residue was purified by silica gel column chromatography (eluent, ethyl acetate: toluene: 1: 20) to obtain the desired compound as a pale yellow viscous liquid in a yield of 5%. By carrying out the resulting compound¹H-NMR measurement. The results are shown in Table 7.

TABLE 6

	Name of Compound	Melting Point (. degree.C.)
			Example 11	Compound 9	158
Example 12	Compound 10	(liquid)
			Example 13	Compound 11	(liquid)

TABLE 7

Industrial applicability

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