TW202110794A - Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing said compound - Google Patents

Abstract

The present invention addresses the problem of providing a compound having high photobase generation efficiency. The present invention is a carbamoyl oxime compound represented by general formula (I). In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 each independently denote a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl oxime group, or the like. At least one of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is a carbamoyl oxime group. The carbamoyl oxime group includes, in the structure thereof, a ring which comprises hydrogen atoms, nitrogen atoms and carbon atoms and in which the number of carbon atoms is 2-10 or a ring which comprises hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms and in which the number of carbon atoms is 2-10.

Description

Carbamethoxime compound and polymerization initiator and polymerizable composition containing the compound

The present invention relates to a carbamethoxime compound.

Generally speaking, a polymerizable composition such as a photosensitive resin composition is formed by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and can be polymerized and cured or developed by irradiating energy rays (light), so It can be used for photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, etc.

The photopolymerization initiator is classified into a photoradical generator, a photoacid generator, and a photobase generator according to the difference in active species generated by irradiation of energy rays (light). The light radical generator has the advantages of faster curing speed and no survival of viable species after curing, but on the other hand, it has the following disadvantages: because the curing is hindered by oxygen, it is necessary to install an oxygen barrier during the curing of the film. Layers and so on. The photoacid generator has the advantage of not being hindered by oxygen, but on the other hand, it has the following disadvantages: the residual acid of the active species corrodes the metal substrate or modifies the hardened resin. Photobase generators have attracted attention because they are not easy to produce the above-mentioned hardening inhibition caused by oxygen and corrosion caused by surviving species. However, in general, there are low sensitivity (low hardening) compared with photoacid generators. problem. The photobase generator is described in Patent Documents 1 and 2, for example. Prior art literature Patent literature

Patent Document 1: US9594302 Patent Document 2: Japanese Patent Laid-Open No. 2013-163670

However, the previous photoalkali generators have low alkali production efficiency and insufficient sensitivity. Therefore, the subject of the present invention is to provide a compound with high photoalkali production efficiency.

The inventors conducted diligent research and found that compounds with specific structures have higher photobase generation efficiency and are useful as polymerization initiators. That is, the present invention is a carbamate compound represented by the following general formula (I).

(式中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R⁹ 及R¹⁰ 分別獨立地表示氫原子、鹵素原子、氰基、硝基、-OR¹¹ 、-COOR¹¹ 、-CO-R¹¹ 、-SR¹¹ 、碳原子數1～20之烴基、碳原子數2～20之含雜環之基、烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基或下述通式(II)所表示之基， R¹¹ 表示氫原子、碳原子數1～20之烴基、碳原子數2～20之含雜環之基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基，於分子中存在複數個R¹¹ 之情形時，其等可相同，亦可不同， R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R⁹ 、R¹⁰ 及R¹¹ 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR¹² 、-COOR¹² 、-CO-R¹² 或-SR¹² 而成之碳原子數1～20之基， R¹² 表示氫原子、碳原子數1～20之烴基、烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基或烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基或羥基而成之碳原子數1～20之基，於分子中存在複數個R¹² 之情形時，其等可相同，亦可不同， ＜群A＞為-O-、-CO-、-COO-、-NR¹³ -、-NR¹³ CO-及-S-， R¹³ 表示氫原子或碳原子數1～20之烴基，於分子中存在複數個R¹³ 之情形時，其等可相同，亦可不同， R¹ 與R² 、R² 與R³ 、R³ 與R⁴ 、R⁴ 與R⁵ 、R⁶ 與R⁷ 、R⁷ 與R⁸ 、R⁸ 與R⁹ 、R⁹ 與R¹⁰ 可分別獨立地相互連結而形成包含氫原子及碳原子之碳原子數3～10之環， R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R⁹ 及R¹⁰ 中之1個以上為下述通式(II)所表示之基， 於分子中存在複數個通式(II)所表示之基之情形時，其等可為相同之基，亦可為不同之基)[化1]

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group,- OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group with 1 to 20 carbon atoms, a heterocyclic ring-containing group with 2 to 20 carbon atoms, and the methylene group in the hydrocarbon group is substituted to be selected from A group with 1 to 20 carbon atoms or a group represented by the following general formula (II) formed from a divalent group in the following <Group A>, R ¹¹ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, A heterocyclic group containing 2 to 20 carbon atoms or a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A> to form a group with 1 to 20 carbon atoms in the molecule When there are a plurality of R ¹¹ , they may be the same or different, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ It may also be a carbon in which one or more of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² A group having 1 to 20 atoms, R ¹² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom in which the methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> One or more of the hydrogen atoms in the 1-20 group or the hydrocarbon group is substituted with a halogen atom, cyano group, nitro group or hydroxyl group, and a group with 1 to 20 carbon atoms exists in the molecule. In ^{the case of R 12} , they can be the same or different. <Group A> is -O-, ^{-CO-, -COO-, -NR 13} -, -NR ¹³ CO- and -S-, and R ¹³ represents When a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms has a plurality of R ¹³ in the molecule, they may be the same or different, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ can be independently connected to each other to form a hydrogen atom and a carbon atom with a carbon number of 3 to Ring 10, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following general formula (II) , When there are multiple groups represented by the general formula (II) in the molecule, they may be the same or different groups)

(式中，R²⁰ 表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群B＞中之二價基而成之碳原子數1～20之基， X¹ 表示-NR²¹ R²² 或下述通式(a)或者下述通式(b)所表示之基， R²¹ 及R²² 分別獨立地表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群B＞中之二價基而成之碳原子數1～20之基， R²⁰ 、R²¹ 及R²² 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR²³ 、-COOR²³ 、-CO-R²³ 或-SR²³ 而成之碳原子數1～20之基， R²³ 表示氫原子、碳原子數1～20之烴基、烴基中之亞甲基被取代為選自下述＜群B＞中之二價基而成之碳原子數1～20之基或烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基或羥基而成之碳原子數1～20之基，於基中存在複數個R²³ 之情形時，其等可相同，亦可不同， ＜群B＞為-O-、-CO-、-COO-、-NR²⁴ -、-NR²⁴ CO-及-S-， R²⁴ 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R²⁴ 之情形時，其等可相同，亦可不同， R²¹ 與R²² 可相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環， n表示0或1， *表示鍵結鍵)[化2]

(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B> ^{X 1 represents -NR 21} R ²² or the group represented by the following general formula (a) or the following general formula (b), R ²¹ and R ²² each independently represent A hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B> to form a group with 1 to 20 carbon atoms, R ²⁰ , R ²¹ and R ²² may also be one or more of the hydrogen atoms in the hydrocarbon group, which are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ R ²³ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, and the methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B> A group with 1 to 20 carbon atoms or one or more of the hydrogen atoms in a hydrocarbon group are substituted with halogen atoms, cyano groups, nitro groups, or hydroxyl groups. The groups have 1 to 20 carbon atoms. When there are a plurality of R ²³ , they may be the same or different. <Group B> is -O-, ^{-CO-, -COO-, -NR 24} -, -NR ²⁴ CO- and -S- , R ²⁴ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R ²⁴ in the group, they may be the same or different. R ²¹ and R ²² may be connected to each other to form a hydrogen atom , Nitrogen atom and carbon atom ring with 2 to 10 carbon atoms or ring containing hydrogen atom, oxygen atom, nitrogen atom and carbon atom with 2 to 10 carbon atoms, n represents 0 or 1, * represents a bonding bond)

(式中，R³¹ 、R³² 、R³³ 、R³⁴ 、R³⁵ 、R³⁶ 、R³⁷ 、R³⁸ 、R³⁹ 及R⁴⁰ 分別獨立地表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群C＞中之二價基而成之碳原子數1～20之基， R³¹ 、R³² 、R³³ 、R³⁴ 、R³⁵ 、R³⁶ 、R³⁷ 、R³⁸ 、R³⁹ 及R⁴⁰ 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR⁴¹ 、-COOR⁴¹ 、-CO-R⁴¹ 或-SR⁴¹ 而成之碳原子數1～20之基， R⁴¹ 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R⁴¹ 之情形時，其等可相同，亦可不同， ＜群C＞為-O-、-CO-、-COO-、-NR⁴² -、-NR⁴² CO-及-S-， R⁴² 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R⁴² 之情形時，其等可相同，亦可不同， R³¹ 與R³² 、R³³ 與R³⁴ 、R³⁵ 與R³⁶ 、R³⁷ 與R³⁸ 、及R³⁹ 與R⁴⁰ 可分別獨立地相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環， *表示鍵結鍵)[化3]

(In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a hydrocarbon group The methylene group in is substituted with a group of 1 to 20 carbon atoms selected from the divalent group in the following <Group C>, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ may also be one or more of the hydrogen atoms in the hydrocarbyl group substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ⁴¹ , -COOR ⁴¹ ,- CO-R ⁴¹ or -SR ⁴¹ is a group with 1 to 20 carbon atoms. R ⁴¹ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R ⁴¹ in the group, they may be The same or different, <group C> is -O-, ^{-CO-, -COO-, -NR 42} -, -NR ⁴² CO- and -S-, R ⁴² represents a hydrogen atom or carbon number 1-20 When there are a plurality of R ⁴² in the base, they may be the same or different, R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ can be independently connected to each other to form a ring with 2-10 carbon atoms containing hydrogen, nitrogen and carbon atoms or 2-10 carbon atoms containing hydrogen, oxygen, nitrogen and carbon atoms The ring, * means bonding bond)

Hereinafter, the present invention will be described in detail. The aminomethoxime compound of the present invention is represented by the above general formula (I). There are geometric isomers due to the double bond of the oxime in the aminoformoxime compound represented by the above general formula (I), but these are not distinguished. That is, in this specification, the amine carboxamide compound represented by the above-mentioned general formula (I), and the following compounds and exemplified compounds which are preferred forms of the compound represent a mixture of isomers or any one of them, and It is not limited to the isomers of the structure shown. Hereinafter, the carboxime 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: fats with 1 to 20 carbon atoms Group hydrocarbon groups and aromatic hydrocarbon groups with 6 to 20 carbon atoms.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, Isopentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl , Dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and other alkyl groups; cyclopentyl, cyclohexyl and other cycloalkyl groups; and cyclohexyl methyl and other cycloalkyl alkanes A group, and an unsaturated aliphatic hydrocarbon group etc. which are a structure in which the carbon-carbon single bond of these groups is substituted with a carbon-carbon double bond or a carbon-carbon triple bond.

As the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms, for example, phenyl, tolyl, xylyl, 2,4,6- mesityl, benzyl, naphthyl, phenanthryl, pyrenyl and biphenyl can be mentioned. Phenyl and so on.

One or more of the hydrogen atoms in the hydrocarbon groups represented by R ¹ to R ¹¹ are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ¹² , -COOR ¹² , -CO-R ^{12 or-} The group of 1-20 carbon atoms formed by SR ^{12 can} be exemplified by one or more of the hydrogen atoms in the above-mentioned hydrocarbon group with 1-20 carbon atoms being substituted with halogen atoms, cyano groups, nitro groups, and hydroxyl groups. , -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² , and the overall number of carbon atoms is 1-20. In addition, as a ^{group with 1 to 20 carbon atoms in which one or two or more of the hydrogen atoms in the hydrocarbon group represented by R 12} is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, the above-mentioned carbon may be mentioned A structure in which one or more of the hydrogen atoms in a hydrocarbon group having 1 to 20 atoms is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and the entire group has 1 to 20 carbon atoms.

The methylene group in the hydrocarbon group represented by R ¹ to R ¹² is substituted with a divalent group selected from the above-mentioned <Group A>, and the group having 1 to 20 carbon atoms includes the above-mentioned carbon number 1 One or more of the methylene groups in the ～20 hydrocarbon groups are substituted with -O-, ^{-CO-, -COO-, -NR 13} -, -NR ¹³ CO- or -S-, and The total number of carbon atoms is 1-20.

One or more of the hydrogen atoms in the hydrocarbon group represented by R ²⁰ to R ²² is substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ^{23 or-} The group formed by SR ²³ with 1 to 20 carbon atoms can be exemplified by one or more of the hydrogen atoms in the above-mentioned hydrocarbon group with 1 to 20 carbon atoms being substituted with halogen atoms, cyano groups, nitro groups, and hydroxyl groups. , -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ , and the overall number of carbon atoms is 1-20. In addition, as a ^{group having 1 to 20 carbon atoms in which one or more of the hydrogen atoms in the hydrocarbon group represented by R 23} is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, the above-mentioned carbon may be mentioned. A structure in which one or more of the hydrogen atoms in a hydrocarbon group having 1 to 20 atoms is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and the entire group has 1 to 20 carbon atoms.

The methylene group in the hydrocarbon group represented by R ²⁰ to R ²³ is substituted with a divalent group selected from the above-mentioned <Group B>, and the group having 1 to 20 carbon atoms includes the above-mentioned carbon number 1 One or more of the methylene groups in the ～20 hydrocarbon groups are substituted with -O-, ^{-CO-, -COO-, -NR 24} -, -NR ²⁴ CO- or -S- and The total number of carbon atoms is 1-20.

One or more of the hydrogen atoms in the hydrocarbon groups represented by R ³¹ to R ⁴⁰ are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ^{41 or-} The group of 1-20 carbon atoms formed by SR ^{41 can} be exemplified by one or more of the hydrogen atoms in the above-mentioned hydrocarbon group with 1-20 carbon atoms being substituted with halogen atoms, cyano groups, nitro groups, and hydroxyl groups. , -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ , and the overall number of carbon atoms is 1-20.

The methylene group in the hydrocarbon group represented by R ³¹ to R ⁴⁰ is substituted with a divalent group selected from the above-mentioned <Group C>, and the group has 1 to 20 carbon atoms, including the above-mentioned carbon number 1 One or more of the methylene groups in the hydrocarbon group of ～20 are substituted with -O-, ^{-CO-, -COO-, -NR 42} -, -NR ⁴² CO- or -S-, and The total number of carbon atoms is 1-20.

Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms in the above general formula (I) include tetrahydrofuranyl, dioxolane, tetrahydropiperanyl, morpholinyl, furanyl, and thienyl groups. , Methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolinyl, pyrazolidinyl, piperidinyl and piperazinyl The base and so on.

In addition, the heterocyclic ring-containing group having 2 to 20 carbon atoms may have a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵⁰ , -COOR ⁵⁰ , -CO-R ⁵⁰ or -SR ⁵⁰ and other substituents. Contains -O-, -CO-, -COO-, -NR ⁵¹ -, -NR ⁵¹ CO- or -S- and other structures. Here, R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group with 1 to 20 carbon atoms represented by R ⁵⁰ and R ⁵¹ corresponds to the number of carbon atoms in the above general formula (I), the above general formula (II), the above general formula (a) and the above general formula (b) The hydrocarbon groups of 1-20 are the same.

^{As R 1} and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ^{9 in the} above general formula (I) , R ⁹ and R ¹⁰ are connected to each other to form a ring containing hydrogen atoms and carbon atoms with 3 to 10 carbon atoms, including: benzene ring, cyclohexene ring, cyclohexane ring, cyclopentadiene ring, ring Pentane ring and so on. In addition, these rings may have a substituent, and examples of the substituent in this case include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.

^{As R 21} and R ²² , R ³¹ and R ³² , R ³³ and R ³⁴ , R ^{35 and R 36} , R ³⁷ and R in the above general formula (II), the above general formula (a) and the above general formula (b) R ³⁸ , R ³⁹ and R ⁴⁰ are connected to each other to form a ring with 2 to 10 carbon atoms including hydrogen atom, nitrogen atom and carbon atom. Examples of the ring including the bonded nitrogen atom include: pyrrole Ring, pyrrolidine ring, imidazole ring, imidazole ring, imidazoline ring, pyrazole ring, pyrazole ring, piperidine ring, piperidine ring, etc. These rings may have a substituent, and examples of the substituent in this case include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.

^{As R 21} and R ²² , R ³¹ and R ³² , R ³³ and R ³⁴ , R ^{35 and R 36} , R ³⁷ and R in the above general formula (II), the above general formula (a) and the above general formula (b) R ³⁸ , R ³⁹ and R ⁴⁰ are connected to each other to form a ring with 2 to 10 carbon atoms containing hydrogen, oxygen, nitrogen and carbon atoms. As a ring including the bonded nitrogen atom, it can be Enumerated: morpholine ring, azole ring, oxazoline ring, oxadiazole ring and the like. These rings may have a substituent, and examples of the substituent in this case include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.

In the present invention, in terms of ease of synthesis, high storage stability, and high alkali production efficiency, it is preferable that either or both ^{of R 3} and R ^{8 in the general formula (I) are} The aminomethyloxime compound represented by the above general formula (II).

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (I) other than the groups represented by the above general formula (II) One or more aminomethoxime compounds of -CO-R ^{11 are} preferred because the obtained polymerizable composition will be cured under low exposure. In particular, ^{the aminomethoxime compound in which R 8} is the group represented by the above general formula (II) and R ³ is -CO-R ¹¹ is also preferable because it is easy to synthesize and has high storage stability. In this case, if R ¹¹ is an aromatic hydrocarbon group with 6 to 20 carbon atoms or a heterocyclic-containing group with 2 to 20 carbon atoms, the obtained polymerizable composition will be cured under low exposure. Therefore, it is preferable, and it is more preferable that R ¹¹ is an aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic ring-containing group having 2 to 10 carbon atoms. Particularly ^{preferably, R 11} is a phenyl group, a tolyl group, a mesityl group, a benzofuran group or a thienyl group.

In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (I) except for the group represented by the above general formula (II) In addition, one or more nitro carboxamide compounds are also preferred because the obtained polymerizable composition will be cured under low exposure. Particularly preferred is an acarboxamide ^{compound in which R 8} is a group represented by the above general formula (II) and R ³ is a nitro group.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, -CO-R ¹¹ , a nitro group, or the general formula (II The amine methoxime compound of) is preferred because of its higher alkali production efficiency.

^{In addition, the amine carboxamide compound in which X 1} in the general formula (II) is -NR ²¹ R ²² is preferred because of its higher alkali production efficiency. It is more preferred that R ²¹ and R ²² are connected to each other to form a hydrogen atom, A nitrogen atom and a carbon atom having a ring with 2 to 10 carbon atoms or a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom having a ring with 2 to 10 carbon atoms. It is particularly ^{preferable that R 21} and R ²² are connected to each other to form a carbon atom ring containing a hydrogen atom, a nitrogen atom, and a carbon atom, and it is more preferable to form a piperidine ring or a pyrrolidine ring.

Furthermore, in the amine carboxamide compound in which ^{X 1} in the general formula (II) is -NR ²¹ R ^{22 , R 21} is a hydrogen atom and R ²² is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ²¹ and R ²² is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, which is also preferred because of its higher alkali production efficiency.

The aminomethoxime compound in which n is 0 in the above general formula (II) is preferred because of its high stability to heat. The aminomethoxime compound in which n is 1 in the above general formula (II) is preferable because the obtained polymerizable composition will be cured under a low exposure amount.

As specific examples of the aminomethoxime compound represented by the above general formula (I), the compounds represented by the following chemical formulas (1) to (62) can be cited. However, the present invention is not limited in any way by the following compounds.

[化4]

[化5]

[化6]

[化7]

[化8]

[化9]

[化10]

[化11]

[化12]

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

(式中，R¹ ～R¹⁰ 、R²⁰ ～R²² 係與上述通式(I)相同)[化13]

(In the formula, R ¹ ～R ¹⁰ , R ²⁰ ～R ²² are the same as the above general formula (I))

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

The amine methyl oxime compound of the present invention efficiently generates alkali and free radicals by light irradiation such as ultraviolet rays or heating, and is therefore useful as a latent base generator and polymerization initiator, and is particularly useful as a latent base generator .

The latent alkali generator of the present invention means a composition containing a compound that has the function of efficiently generating alkali by irradiating light such as ultraviolet rays, and the use of the composition includes a pH adjusting agent , The use of alkali catalysts, etc.

In addition, the aminomethoxime compound of the present invention has a higher efficiency in generating bases and free radicals caused by light irradiation among the above-mentioned polymerization initiators, so it functions as a photobase generator and photoradical polymerization. The starter is useful, and because the alkali production efficiency is very high, it is especially useful as a photoalkali generator.

The polymerization initiator of the present invention contains at least one carboxime compound represented by the above-mentioned general formula (I). The polymerization initiator that can be used in combination with the aminoformoxime compound represented by the above general formula (I) is not particularly limited, and the previously known photobase generators and photoradical polymerization initiators can be cited.

Regarding the content of the compound represented by the general formula (I) in the polymerization initiator, it is preferably 1-100% by mass in terms of the obtained polymerizable composition curing at a low exposure amount. More preferably, it is 50 to 100% by mass.

The polymerizable composition of the present invention contains a polymerization initiator (A) and a polymerizable compound (B) having at least one type of amine oxime compound represented by the above-mentioned general formula (I). Regarding the content of the polymerization initiator (A), it is preferably 1-20 mass parts relative to 100 mass parts of the polymerizable compound (B) in terms of the obtained polymerizable composition curing at a low exposure dose Parts, more preferably 1-10 parts by mass. By setting the content of the polymerization initiator (A) to 1 part by mass or more, it is easy to prevent poor curing caused by insufficient curing sensitivity. Therefore, it is preferably set to 20 parts by mass or less to suppress light irradiation or heating The volatile matter of time is better.

Examples of the polymerizable compound (B) used in the present invention include: a compound having an anionic polymerizable functional group, a compound that is cured by a reaction in which a base acts as a catalyst or a reaction in which the base is added, and free The base polymerizable compound is preferably a photosensitive resin that is polymerized and cured by irradiating energy rays such as ultraviolet rays, or the curing temperature is lowered from the viewpoint that the obtained polymerizable composition will be cured under low exposure. The hardening resin. The aforementioned anionic polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator using active energy rays such as ultraviolet rays, and examples include epoxy groups, episulfide groups, and cyclic monomers. Body (σ-valerolactone, ε-caprolactone), malonate, etc. As a reaction in which a base acts as a catalyst or a reaction in which a base undergoes addition, examples include: urethane bond formation reaction by isocyanate and alcohol, addition reaction of a compound containing epoxy resin and hydroxyl group, Addition reaction of compounds containing epoxy resin and carboxylic acid group, addition reaction of epoxy resin and thiol compound, Michael addition reaction of (meth)acrylic acid group, dehydration condensation reaction of polyamide acid, alkane Hydrolysis/condensation reaction of oxysilane, etc.

Examples of compounds having anionic polymerizable functional groups include epoxy resins, oxetane resins, episulfide resins, cyclic amides (lactone compounds), and cyclic esters (lactone compounds) , Cyclic carbonate-based compounds, malonic acid esters, etc. Examples of compounds that are cured by a reaction in which a base acts as a catalyst or a reaction in which the base is added include: polyamide resin (polyimination reaction by dehydration and cyclization), epoxy・Hydroxy group (ring-opening addition reaction), epoxy group, carboxylic acid system (ring-opening addition reaction), epoxy group, mercaptan system (ring-opening addition reaction), epoxy group, acid anhydride system (ring-opening Polycondensation), cyanate ester (tricyclic cyclization reaction), cyanate ester, epoxy type (cyclization reaction), cyanate ester, maleimide type (crosslinked copolymerization), oxetane, hydroxyl System (ring-opening addition reaction), oxetane, carboxylic acid system (ring-opening addition reaction), oxetane, mercaptan system (ring-opening addition reaction), oxetane, acid anhydride System (ring-opening polycondensation), episulfide, hydroxyl system (ring-opening addition reaction), episulfide, carboxylic acid system (ring-opening addition reaction), episulfide, mercaptan system (ring-opening addition reaction) , Episulfide and acid anhydride series (ring-opening polycondensation), acrylic acid and mercaptan series (Miccan addition reaction), methacrylic acid and mercaptan series (Miccan addition reaction), acrylic acid and amine series (Miccan addition reaction) Reaction), methacrylic acid, amine system (Miccan addition reaction), carboxylic acid, hydroxyl system (polyesterification reaction), carboxylic acid, amine system (polyamide reaction), isocyanate, hydroxyl system (polyamine Formate reaction), isocyanate/thiol series (polythiocarbamation reaction), alkoxysilane series (hydrolysis and polycondensation), etc. Examples of the compound that undergoes radical polymerization include ethylenically unsaturated compounds. In terms of higher reactivity, it is preferable to use a compound that undergoes radical polymerization. These resins may be used alone or in combination of two or more kinds. As a preferred combination, in terms of rapid reaction progress or good adhesion, a combination of epoxy resin and phenol resin can be cited, and a combination of epoxy resin and thiol compound in terms of excellent low-temperature curability In terms of higher reactivity, a combination of ethylenically unsaturated compounds and thiol compounds can be cited.

The above-mentioned epoxy resin only needs to have an epoxy group, except for the carbamate compound of the present invention. Examples of epoxy resins include polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, catechol, and phloroglucinol; dihydroxy naphthalene, biphenol, methylene Bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, sub Isopropyl bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1, 1,3-Tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol Polyglycidyl ether of polynuclear polyphenol compounds such as novolac, o-cresol novolac, ethyl phenol novolac, butylphenol novolac, octylphenol novolak, resorcinol novolak, terpene phenol and other polynuclear polyphenol compounds Compounds; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyglycol, thiodiethanol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Polyglycidyl ether such as polyols; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, two Polyacid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid Glycidyl esters of aliphatic, aromatic or cycloaliphatic polybasic acids such as formic acid and endomethylene tetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N,N-di Glycidyl aniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl o-toluidine and other epoxy compounds with glycidyl amino groups; vinyl ring Hexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6- The epoxides of cyclic olefin compounds such as methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; Epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, epoxidized styrene-butadiene copolymer, and heterocyclic rings such as triglycidyl isocyanurate Compound. In addition, these epoxy resins may also be formed by internal crosslinking of prepolymers of blocked isocyanates, or may be formed by using multiple active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphates, etc.) High molecular weight. Among the above-mentioned epoxy resins, in terms of excellent curability of the obtained polymerizable composition, those having a glycidyl group are preferred, and those having a glycidyl group having a bifunctional or more are more preferred.

The said phenol resin should just have a phenolic hydroxyl group, but the said carbamate compound and epoxy resin are excluded. As the phenol resin, in terms of excellent curability of the obtained polymerizable composition, a phenol resin having two or more hydroxyl groups per molecule is preferred, and generally known ones can be used. Examples of phenol resins include: bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak type resin, bisphenol A novolak type phenol Resin, glycidyl ester type phenol resin, aralkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, multifunctional phenol resin, naphthol resin, naphthol novolak resin , Multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl Type phenol resins, alicyclic phenol resins, polyol type phenol resins, phosphorus-containing phenol resins, polymerizable unsaturated hydrocarbon group-containing phenol resins, and hydroxyl group-containing silicone resins are not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types.

The above-mentioned thiol compound should just have a thiol group, except for the above-mentioned carbamate compound, epoxy resin, and phenol resin. Among the thiol compounds, those having two or more thiol groups in one molecule are preferable in terms of excellent curability of the obtained polymerizable composition. As preferred specific examples of the thiol compound, bis(2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis(mercaptomethyl)benzene , 1,4-bis(mercaptomethyl)benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto -3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl- 1,11-Dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, 1,1,3,3-tetra(mercaptomethyl Thiol) propane, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoglycolate, trimethylolpropane mercaptoglycolate, and trimethylolpropane trimercaptopropionate, more preferably listed: 1,2 ,6,7-Tetramercapto-4-thiaheptane, pentaerythritol, 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 tetramercaptoglycolate. Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, bis(2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiol Alkanes, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. A thiol compound can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyamide resin include ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexane, which are acid dianhydrides. Tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, etc. as raw materials and used as diamines (ortho, meta or p) phenylenediamine, (3,3'- or 4,4'-) diamino diphenyl ether, diamino diphenyl Methyl ketone, (3,3'- or 4,4'-) diaminodiphenylmethane and other resins are used as raw materials.

Examples of the polyurethane resin include polyfunctional isocyanates such as toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and polyether polyols, polyester polyols, etc. Polycarbonate polyols and other polyols (polyfunctional alcohols) are used as raw materials for resins, etc. Moreover, as said nylon resin, the resin etc. which use cyclic monomers, such as ε-caprolactam and dodecanolide as a raw material, are mentioned. Moreover, as the said polyester resin, the resin etc. which use cyclic monomers, such as δ-valerolactone and β-propiolactone, as a raw material, etc. are mentioned.

The above-mentioned ethylenically unsaturated compound should just have an ethylenically unsaturated bond, except for the above-mentioned carbamate compounds, epoxy resins, phenol resins, and thiol compounds. Examples of ethylenically unsaturated compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid Acid, mesaconic acid, mono[2-(meth)acryloxyethyl] succinate, mono[2-(meth)acryloxyethyl] phthalate, ω-carboxyl poly Caprolactone mono(meth)acrylate and other mono(meth)acrylates of polymers with carboxyl and hydroxyl groups at both ends; hydroxyethyl (meth)acrylate maleate, (meth)acrylic acid Hydroxypropyl, maleate, dicyclopentadiene, maleate, or multifunctional (meth)acrylate with one carboxyl group and two or more (meth)acrylic acid groups, etc. Saturated polybasic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate , Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate Base) isononyl acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, (meth)acrylate Base) dimethylaminoethyl acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, (meth)acrylic acid Poly (ethoxy) ethyl, butoxy ethoxy ethyl (meth) acrylate, ethyl hexyl (meth) acrylate, phenoxy ethyl (meth) acrylate, tetrahydrofuran (meth) acrylate Ester, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-Hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, isocyanurate tri[( Ester of unsaturated monobasic acid and polyhydric alcohol or polyphenol such as meth)acryloyl ethyl) ester, polyester (meth)acrylate oligomer; zinc (meth)acrylate, magnesium (meth)acrylate, etc. Metal salts of unsaturated polybasic acids; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride , 5-(2,5-dioxotetrahydrofuranyl) -3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl bicyclic Anhydrides of unsaturated polybasic acids such as heptenedicarboxylic acid anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriamine tri(meth)acrylamide, benzene Dimethylbis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide and other unsaturated monobasic acids and polyamines such as amides; acrolein and other unsaturated Aldehydes; (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide and other unsaturated nitriles; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methyl Oxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl Unsaturated aromatic compounds such as methyl methyl ether and vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amines such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine Compounds; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether and other vinyl ethers; maleimide , N-phenyl maleimide, N-cyclohexyl maleimide and other unsaturated imines; indene, 1-methylindene and other indenes; 1,3-butadiene , Isoprene, chloroprene and other aliphatic conjugated dienes; polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, polysiloxane equal polymers Macromonomers with a single (meth)acrylic acid group at the end of the molecular chain; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, iso Triallyl cyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl-containing vinyl monomer and polyisocyanate compound amine Vinyl epoxy compounds such as vinyl formate compounds, hydroxyl-containing vinyl monomers and polyepoxy compounds. The ethylenically unsaturated compound can be used alone or in combination of two or more kinds.

As the above-mentioned ethylenically unsaturated compounds, commercially available products can also be used, for example: Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (the above are manufactured by Nippon Kayaku ); ARONIX M-215, M-350 (manufactured by Toagosei above); NK ESTER A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (the above are made by Shinnakamura Chemical Industry Co., Ltd.); SPC-1000, SPC-3000 (manufactured by Showa Denko), etc.

The content of the polymerizable composition (B) only needs to be an amount suitable for the purpose of use. In order to prevent poor curing, it is preferably 50% by mass in the solid content (total components other than the solvent) in the polymerizable composition. It is contained in the form of more than 60 parts by mass, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more.

The polymerizable composition of the present invention may use additives such as inorganic compounds, colorants, latent epoxy hardeners, chain transfer agents, sensitizers, solvents, etc., as optional components.

Examples of the above-mentioned inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon dioxide, and aluminum oxide; layered clay minerals, rice Lori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder (especially glass paste), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, silicic acid Aluminum, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds can be used as fillers, anti-reflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink-generating agents, etc., for example.

Examples of the aforementioned colorants include pigments, dyes, natural pigments, and the like. These color materials can be used alone or in a mixture of two or more.

化合物；喹啉化合物；蒽醌化合物；香豆素化合物；酞菁化合物；異吲哚啉酮化合物；異吲哚啉化合物；喹吖啶酮化合物；蒽締蒽酮化合物；芘酮化合物；苝化合物；吡咯并吡咯二酮化合物；硫靛化合物；二㗁𠯤化合物；三苯甲烷化合物；喹酞酮化合物；萘四羧酸；偶氮染料、花青染料之金屬錯合物化合物；色澱顏料；藉由爐排法、導槽法或熱分析法所獲得之碳黑或乙炔黑、科琴黑或燈黑等碳黑；利用環氧樹脂對上述碳黑進行調整或被覆而成者、預先於溶劑中利用樹脂對上述碳黑進行分散處理而使之吸附20～200 mg/g之樹脂而成者、對上述碳黑進行酸性或鹼性表面處理而成者、平均粒徑為8 nm以上且DBP(Dibutyl Phthalate，鄰苯二甲酸二丁酯)吸油量為90 ml/100 g以下之碳黑、表面積每100 m² 根據950℃下之揮發成分中之CO及CO₂ 算出之總氧氣量為9 mg以上之碳黑；石墨、石墨化碳黑、活性碳、碳纖維、奈米碳管、螺旋碳纖維、碳奈米角、碳氣凝膠、富勒烯；苯胺黑、顏料黑7、鈦黑；氧化鉻綠、米洛麗藍、鈷綠、鈷青、錳系、亞鐵氰化物、磷酸鹽群青、鐵藍、群青、天藍、濃綠色、翡翠綠、硫酸鉛、黃丹、鋅黃、鐵丹(紅色氧化鐵(III))、鎘紅、合成鐵黑、棕土等有機或無機顏料。該等顏料可單獨使用或將複數種混合使用。As the above-mentioned pigments, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds; 𠮿

Compounds; Quinoline Compounds; Anthraquinone Compounds; Coumarin Compounds; Phthalocyanine Compounds; Isoindolinone Compounds; Isoindoline Compounds; Quinacridone Compounds; Anthroneanthone Compounds; Pyrene Compounds; Perylene Compounds ; Dione pyrrolopyrrole compound; thioindigo compound; diphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; metal complex compound of azo dye and cyanine dye; lake pigment; Carbon black, acetylene black, Ketjen black, or lamp black obtained by grate method, channel method or thermal analysis method; the carbon black is adjusted or coated with epoxy resin, and the above-mentioned carbon black is adjusted or coated in advance. It is obtained by dispersing the above-mentioned carbon black with resin in a solvent to adsorb 20-200 mg/g of resin, or after performing acidic or alkaline surface treatment on the above-mentioned carbon black, with an average particle size of 8 nm or more and DBP (Dibutyl Phthalate, dibutyl phthalate) carbon black with an oil absorption of 90 ml/100 g or less, the total oxygen content calculated _{from the CO and CO 2} in the volatile components at 950℃ ^{per 100 m 2 of surface area is} Carbon black above 9 mg; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black ; Chromium oxide green, Miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, iron blue, ultramarine, sky blue, dark green, emerald green, lead sulfate, yellow red, zinc yellow, Iron red (red iron oxide (III)), cadmium red, synthetic iron black, umber and other organic or inorganic pigments. These pigments can be used alone or in a mixture of plural kinds.

As the above-mentioned pigments, commercially available pigments can also be used, for example: Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 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.

染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁𠯤染料、酞菁染料、花青染料等染料等；該等亦可混合複數種來使用。Examples of the above-mentioned dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, and

Dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, alizarin dyes, phthalocyanine dyes, cyanine dyes, etc.; It can also be used by mixing plural kinds.

Examples of the above-mentioned latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazines, 4,4'-diaminodiphenyl sulfides, boron trifluoride amine complex salts, imidazoles, Guanamines, imidazoles, ureas, melamine, etc.

、二異丙基9-氧硫𠮿

、下述化合物No.C1、三巰基丙酸三(2-羥基乙基)異氰尿酸酯等脂肪族多官能硫醇化合物、昭和電工公司製造之Karenz MT BD1、PE1、NR1等。As the above-mentioned chain transfer agent or sensitizer, a sulfur atom-containing compound can usually be used. Examples include: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycamine Acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminomethanyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-( 3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylsulfanyl) phenyl ether, 2-mercaptoethanol , 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole , 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate) and other mercapto compounds, make The disulfide compound obtained by oxidation of the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropane three (3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexamethylene dithiol, decane dithiol, 1,4-dimethylmercaptobenzene, butanediol dimercaptopropane Esters, butanediol bismercaptoglycolate, ethylene glycol bismercaptoglycolate, trimethylolpropane trimercaptoglycolate, butanediol bismercaptopropionate, trimethylolpropane trimercaptopropionic acid Esters, trimethylolpropane trimercaptoglycolate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoglycolate, trihydroxyethyl trimercaptopropionate, diethyl 9-oxythio𠮿

, Diisopropyl 9-oxysulfur 𠮿

, The following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionate tris(2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation.

[Chemical Formula 14] Compound No.C1

As the above-mentioned solvent, it is usually possible to use: solvents that can dissolve or disperse the above-mentioned components (polymerization initiator (A) and polymerizable compound (B), etc.), such as methyl ethyl ketone, methyl amyl ketone, and diethyl ketone. Ethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; diethyl ether, diethane, tetrahydrofuran, 1,2-dimethoxyethane , 1,2-diethoxyethane, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate , Ethyl lactate, dimethyl succinate, TEXANOL and other ester solvents; γ-caprolactone, δ-caprolactone, γ-butyrolactone and other ester solvents; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as monoethyl ether; alcohol solvents such as methanol, ethanol, iso-or n-propanol, iso-or n-butanol, pentanol, etc.; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetic acid Ester, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate and other ether ester solvents; benzene, toluene , Xylene and other BTX solvents; hexane, heptane, octane, cyclohexane and other aliphatic hydrocarbon solvents; turpentine, D-limonene, pinene and other terpene hydrocarbon oils; mineral spirits, Swazol#310( Cosmo Songshan Petroleum (stock)), Solvesso#100 (Exxon Chemical (stock)) and other alkane solvents; carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane and other halogenated fats Group hydrocarbon solvents; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N- Dimethyl acetamide; N-methyl pyrrolidone; dimethyl sulfide; water, etc.; these solvents can be used in the form of one kind or a mixed solvent of two or more kinds. Among them, ketone or ether ester solvents, especially propylene glycol-1-monomethyl ether-2-one can be preferably used in terms of alkali developability, graphics, film-forming properties, and solubility. Acetate (hereinafter, also referred to as "PGMEA") or cyclohexanone. In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, as long as the amount of the solvent is such that the components are uniformly dispersed or dissolved and the polymerizable composition of the present invention is in a liquid or paste state suitable for each application. However, it is generally preferable that the amount of the solid content (total components other than the solvent) in the polymerizable composition of the present invention is within the range of 10 to 90% by mass to obtain a uniform cured product.

In addition, the polymerizable composition of the present invention can also improve the properties of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (Meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene) Resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, etc. In the case of using the above-mentioned organic polymer, the content is preferably 10 to 500 parts by mass relative to 100 parts by mass of the polymerizable compound (B) in terms of excellent curability of the obtained polymerizable composition.

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

As the above-mentioned surfactants, fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; and anionic interfaces such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates can be used. Active agent; cationic surfactants such as higher amine halide, quaternary ammonium salt; polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, monoglycerin fatty acid ester, etc. Nonionic surfactants; amphoteric surfactants; surfactants such as silicone surfactants; these can also be used in combination.

As the above-mentioned silane coupling agent, for example, the silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc. having isocyanate groups, methacrylic groups or epoxy groups can be preferably used. Base silane coupling agent.

Examples of the above-mentioned melamine compound include (poly)methylol melamine, (poly)methylol glycoluril, (poly)methylol benzoguanidine, (poly)methylolurea and other nitrogen compounds, which are active methylol groups. (CH ₂ OH group) All or a part (at least 2) of the compound is etherified with an alkyl group, etc. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, or a butyl group; they may be the same or different from each other. In addition, the methylol group that has not been etherified with the alkyl group can condense itself in one molecule, or condense between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among them, in terms of solubility in solvents and difficulty in crystallizing from polymerizable compositions, melamine etherified with alkyl groups such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred. .

In the polymerizable composition of the present invention, the content of any components other than the polymerization initiator (A) and the polymerizable compound (B) (excluding inorganic compounds, colorants, and solvents) is appropriately selected depending on the purpose of use There is no particular limitation. In terms of excellent curability of the obtained 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 energy rays to form a cured product. The hardened product is formed into an appropriate shape corresponding to the application. For example, in the case of forming a film-like cured product, the polymerizable composition of the present invention can be used with a spin coater, roll coater, bar coater, die nozzle coater, curtain coater, Various known mechanisms such as printing and dipping are applied to support substrates such as soda glass, quartz glass, semiconductor substrate, metal, paper, and plastic. In addition, it can also be temporarily performed on a supporting substrate such as a film and then transferred to another supporting substrate, and the application method is not limited.

As a light source of energy rays that can be used to harden the polymerizable composition of the present invention, it can be used from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, and metal Halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc. obtain electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms or high energy such as electron beams, X-rays, and radiation In terms of the excellent curability of the obtained polymerizable composition, it is preferable to use an ultra-high pressure mercury lamp, mercury vapor arc lamp, carbon arc lamp, xenon arc lamp, etc. that emit light with a wavelength of 300 to 450 nm. .

Furthermore, by using laser light as the exposure light source, the direct laser drawing method that directly forms an image based on digital information such as a computer without using a mask will not only improve productivity, but also improve resolution or position accuracy, which is useful. As the laser light, light with a wavelength of 340 to 430 nm can be preferably used, and excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers can also be used Lasers, various semiconductor lasers and YAG (Yttrium Aluminum Garnet, Yttrium Aluminum Garnet) lasers that emit light in the visible to infrared range. In the case of using these laser lights, it is preferable to add a sensitizing dye that absorbs in the visible to infrared region in terms of the excellent curability of the obtained polymerizable composition.

In addition, when the polymerizable composition of the present invention is cured, it is usually necessary to heat it after the above-mentioned energy rays are irradiated. In terms of the curing rate, heating at about 40 to 150°C is preferred.

The polymerizable composition of the present invention can be used in various applications such as the following: photocurable paints or varnishes; photocurable adhesives; coating agents for metals; printed circuit boards; color televisions, PC (Personal Computer) monitors , Color filters in liquid crystal display elements for color displays such as portable information terminals and digital cameras; color filters in CCD (CCD, charge coupled device) image sensors; electrode materials for plasma display panels; powder Coating; Printing Ink; Printing Plate; Adhesive; Dental Composition; Gel Coating; Photoresist for Electronic Engineering; Electroplating Resist; Etching Resist; Dry Film; Solder Resist; Manufacture of color filters for various display purposes or resists used in the manufacturing steps of plasma display panels, electroluminescent display devices, and LCD (Liquid Crystal Display, liquid crystal display devices) to form their structures; Composition for encapsulating electrical and electronic parts; solder resist; magnetic recording materials; small mechanical parts; optical waveguides; optical switches; masks for plating; etching masks; color test systems; glass fiber cable coatings; screen plates Templates for printing; materials for producing three-dimensional objects by stereolithography; materials for holographic recording; image recording materials; microelectronic circuits; decolorizing materials; decolorizing materials for image recording materials; using microcapsules Decolorizing materials for image recording materials; photoresist materials for printed wiring boards; photoresist materials for UV (ultraviolet) and visible light laser direct imaging systems; the formation of dielectric layers in successive layers of printed circuit boards The use of the photoresist material or protective film used is not particularly limited.

The polymerizable composition of the present invention can also be used to form spacers for liquid crystal display panels and to form protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertical alignment type liquid crystal display elements.

The above-mentioned spacers for liquid crystal display panels are preferably formed by the following steps: (1) a step of forming a coating film of the polymerizable composition of the present invention on a substrate; (2) a mask having a specific pattern shape is interposed The step of irradiating the coating with energy rays (light); (3) the baking step after exposure; (4) the step of developing the exposed coating; and (5) the step of heating the developed coating step.

The polymerizable composition of the present invention added with a colorant can be preferably used as a resist for each pixel such as RGB (Red-Green-Blue, red-green-blue) in a color filter or as a resist for forming each pixel Resist for the black matrix of the partition wall. Furthermore, when the black matrix resist of the ink repellent is added, it can be preferably used as a partition wall for an inkjet type color filter with a distribution angle of 50° or more. As the ink repellent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant can be preferably used.

In the case of using the above-mentioned inkjet type color filter partition wall, the optical element is manufactured by the following method: the partition wall formed of the polymerizable composition of the present invention is divided on the to-be-transferred body, and the partition wall is formed by inkjet The method applies droplets to the divided recesses on the transferred body to form an image area. In this case, it is preferable that the droplet contains a coloring agent to color the image area. In this case, the optical element produced by the above-mentioned manufacturing method has at least a pixel group including a plurality of colored areas on the substrate and will The partition wall separating each colored area of the pixel group.

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, it may contain ultraviolet absorbers, alkylated modified melamine and/or acrylic modified melamine, 1 or 2 functional (meth)acrylate monomers containing alcoholic hydroxyl groups in the molecule, and/or silica sol .

The above-mentioned insulating film can be used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a support base that can be peeled. If the laminate system can be developed by an alkaline aqueous solution, the thickness of the insulating resin layer is preferably 10 ~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 to form fired product patterns such as partition wall patterns, dielectric patterns, electrode patterns, and black matrix patterns of plasma display panels. [Example]

Hereinafter, the present invention will be described in further detail with examples and comparative examples, but the present invention is not limited to these examples and the like. The compound obtained below is "liquid" means that it is liquid at 25°C under atmospheric pressure.

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

[化15]

(Synthesis of oxime 1) Add 1.0 eq. of 2-(4-((4-(2-methylbenzyl)phenyl)thiol)phenyl)acetonitrile and 1.0 eq. of sodium hydroxide to a 100 ml four-necked flask, and dissolve Stir in ethanol (100% by weight of the theoretical yield) on an ice bath at 5°C. To this, 1.0 eq. of isobutyl nitrite dissolved in ethanol (100% by weight of the theoretical output) was added dropwise. After returning the reaction solution to room temperature and stirring for 2 hours, it was filtered and the filtrate was concentrated. Ethyl acetate was added thereto, washed with ion-exchanged water three times, dried with magnesium sulfate, and concentrated again. The residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane=1:5), and the target compound was obtained as a brown viscous liquid compound with a yield of 60%.

(Synthesis of Compound 1) To a 100 ml four-necked flask, add 1.0 eq. of oxime body 1, 1.0 eq. of dichloromethane (500% by weight of theoretical output), and 2.0 eq. of triethylamine, and stir at 5°C on an ice bath . What was obtained by dissolving 1.1 eq. of 4-nitrophenyl chloroformate in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 5°C on an ice bath again, 1.1 eq. of piperidine was added dropwise. After stirring for 3 hours at room temperature, the solvent was distilled off under reduced pressure. Ethyl acetate and 5 mass% NaOH aqueous solution were added to this, and oil-water separation was performed. Furthermore, the organic layer was washed three times with ion-exchanged water, and then concentrated. Ethanol was added to the residue for crystallization, and the target compound was obtained as a pale yellow powdery compound with a yield of 79%. The obtained compound was subjected to TG-DTA (Thermo-Gravimetric-Differential Thermal analysis) (melting point) measurement and ¹ H-NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) measurement. The results are shown in Table 1 and Table 2, respectively.

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

[化16]

(Synthesis of oxime 2) Add 2,2,2-trifluoro-1-(4-((4-(2-methylbenzyl)phenyl)thio)phenyl)ethane-1- Ketone 1.0 eq. was dissolved in ethanol (600% by weight of theoretical output). Add 1.2 eq. of hydroxylammonium chloride and 3.0 eq. of pyridine to the solution. The reaction mixture was refluxed for 3 hours, and the solvent was distilled off under reduced pressure. Ion-exchanged water was added thereto, and extraction was performed with ethyl acetate. The organic layer was washed in the order of 5% by mass hydrochloric acid and ion-exchanged water, and dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane=1:5), and the target compound was obtained as a brown viscous liquid compound with a yield of 76%.

(Synthesis of Compound 2) Except that the oxime body 1 was changed to the oxime body 2, the same operation as in Example 1 was carried out to the water washing step. The concentrated residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane=1:5), and the target compound was obtained as a yellow viscous liquid compound with a yield of 76%. The obtained compound was subjected to ¹ H-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.

[化17]

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

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

[化18]

(Synthesis of oxime 4) Add 1.0 eq. of 1-(4-((4-nitrophenyl)thio)phenyl)dodecane-1-one to a 100 ml four-necked flask and dissolve it in dimethylformamide ( 300% by weight of theoretical output). Add 3.2 eq. of hydroxylammonium chloride and 3.2 eq. of sodium hydroxide to the solution. The reaction mixture was heated and stirred at 65°C for 2 hours, ion-exchanged water was added, and extraction was performed with ethyl acetate. Furthermore, after washing 3 times with ion-exchanged water, the organic layer was dried and concentrated with magnesium sulfate, and the residue was subjected to silica gel column chromatography (eluent = ethyl acetate: hexane = 1:10) refined. Thereby, the target compound as a light yellow solid compound was obtained with a yield of 61%.

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

[化19]

(Synthesis of oxime 5) Add 1.0 eq. of 1-(4-((4-nitrophenyl)thio)phenyl)dodecane-1-one to a 100 ml four-necked flask and dissolve it in THF (Tetrahydrofuran, tetrahydrofuran) ( 350% by weight of theoretical output). 1.0 eq. of 4M·HCl-ethyl acetate and 1.2 eq. of isobutyl nitrite were added thereto, and stirred at 35°C for 3 hours. Methyl isobutyl ketone was added to the reaction liquid, washed with ion-exchanged water 6 times, and then dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent = ethyl acetate: hexane = 1: 8). Thereby, the target product as a light brown liquid compound was obtained with a yield of 86%.

(Synthesis of Compound 5) Except for changing the oxime body 1 to the oxime body 5, the same operation as in Example 1 was carried out to the water washing step. It was concentrated, and the target compound was obtained as a brown liquid compound with a yield of 41%. The obtained compound was subjected to ¹ H-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.

[化20]

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

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

[化21]

(Synthesis of oxime 6) Add 1.0 eq. of 1-(4-((4-(thiophen-2-carbonyl)phenyl)thio)phenyl)ethane-1-one to a 100 ml four-necked flask and dissolve it in dimethyl Formamide (400% by weight of theoretical yield). Add 1.1 eq. of hydroxylammonium chloride and 1.1 eq. of pyridine to the solution. The reaction mixture was heated and stirred at 55°C for 2 hours. Ethyl acetate (400% by weight of the theoretical output) was added to the reaction solution, and ion-exchanged water (800% by weight of the theoretical output) was added dropwise to perform crystallization, and the target product was obtained with a yield of 89%.

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

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

[化22]

(Synthesis of oxime 7) Add 3-cyclohexyl-1-(4-((4-(2-methylbenzyl)phenyl)thio)phenyl)propane-1-one 1.0 eq. to a 100 ml four-necked flask, Dissolve it in dimethylformamide (300% by weight of theoretical yield). Add 1.1 eq. of hydroxylammonium chloride and 1.1 eq. of pyridine to the solution. The reaction mixture was heated and stirred at 60°C for 3 hours, ion-exchanged water was added, and extraction was performed with ethyl acetate. Furthermore, after washing with ion-exchanged water three times, the organic layer was dried and concentrated with magnesium sulfate, and the residue was analyzed by silica gel column chromatography (eluent = ethyl acetate: hexane = 1:8) Refined. Thereby, the target compound as a light yellow solid compound was obtained with a yield of 60%.

(Synthesis of Compound 8) Except for changing oxime body 1 to oxime body 7, the same operation as in Example 1 was carried out to the water washing step. It was concentrated, and the target compound was obtained as a light brown liquid compound with a yield of 50%. The obtained compound was subjected to ¹ H-NMR measurement. The results are shown in Table 2.

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

[化23]

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

[Table 1] Compound name Melting point (℃) 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] Chemical shift/ppm (multiplicity, number of protons) Compound 1 (CDCl ₃ , 400 MHz) 7.91 (d, 2H), 7.75 (d, 2H), 7.43 (d, 2H), 7.41-7.38 (m, 3H), 7.31-7.24 (m, 3H), 3.63-3.55 (m, 4H), 2.34 ( s, 3H), 1.68-1.63 (m, 6H) Compound 2 (CDCl ₃ , 400 MHz) 7.74 (d, 2H), 7.50 (d, 2H), 7.44-7.34 (m, 5H), 7.30-7.24 (m, 3H), 3.47 (t, 2H), 3.13 (t, 2H), 2.34 (s, 3H), 1.60-1.40 (m, 6H) Compound 3 (CDCl ₃ , 400 MHz) 7.99 (d, 2H), 7.70-7.80 (m, 3H), 7.63 (d, 1H), 7.45-7.55 (m, 4H), 7.30-7.40 (m, 3H), 3.50-3.60 (m, 4H), 2.75-2.85 (m, 2H), 1.55-1.70 (m, 7H), 1.45-1.55 (m, 2H), 0.95 (d, 6H) Compound 4 (CDCl ₃ , 400 MHz) 8.09 (d, 2H), 7.79 (d, 2H), 7.53 (d, 2H), 7.23 (d, 2H), 3.45-3.60 (m, 4H), 2.81 (t, 2H), 1.55-1.65 (m, 8H), 1.20-1.35 (m, 16H), 0.87 (t, 3H) Compound 5 (CDCl ₃ , 400 MHz) 8.10-8.20 (m, 4H), 7.49 (d, 2H), 7.39 (d, 2H), 3.50-3.55 (m, 4H), 2.76 (t, 2H), 1.55-1.70 (m, 8H), 1.20- 1.35 (m, 14H), 0.88 (t, 3H) Compound 6 (CDCl ₃ , 400 MHz) 8.10-8.20 (m, 4H), 7.49 (d, 2H), 7.39 (d, 2H), 3.25-3.40 (m, 4H), 2.75 (t, 2H), 1.55-1.65 (m, 6H), 1.20- 1.40 (m, 18H), 0.85-1.00 (m, 9H) Compound 7 (CDCl ₃ , 400 MHz) 7.75-7.80 (m, 4H), 7.73 (d, 1H), 7.64 (d, 1H), 7.48 (d, 2H), 7.32 (d, 2H), 7.16 (t, 1H), 3.10-3.20 (m, 4H), 2.36 (s, 3H), 1.55-1.75 (m, 4H), 1.30-1.40 (m, 4H), 0.95 (t, 6H) Compound 8 (CDCl ₃ , 400 MHz) 7.80 (d, 2H), 7.60 (d, 2H), 7.35 (d, 2H), 7.40-7.30 (m, 3H), 7.30-7.20 (m, 3H), 3.55-3.40 (m, 4H), 2.70 ( t, 2H), 2.34 (s, 3H), 1.60-1.40 (m, 19H) Comparative compound 1 (CDCl ₃ , 400 MHz) 7.81 (d, 2H), 7.73 (d, 1H), 7.70-7.60 (m, 3H), 7.49 (d, 2H), 7.39 (d, 2H), 7.17 (t, 1H), 6.38 (br, 1H) , 3.30-3.40 (m, 2H), 2.43 (s, 3H), 1.55-1.70 (m, 2H), 1.35-1.45 (m, 2H), 0.93 (t, 3H)

[Examples 9 and 10 and Comparative Examples 2 and 3] Adjustment of polymerizable composition The formulation described in Table 3 was performed to obtain polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2. Furthermore, the blending values in the table represent parts by mass. In addition, the symbols of each component in the table indicate 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 (phenolic novolac type epoxy resin, epoxy equivalent 193 g/eq., manufactured by Nippon Kayaku Co., Ltd.) B-2: H-3M (phenol resin, hydroxyl equivalent 105～109 g/eq., manufactured by Meiwa Chemical Co., Ltd.) C-1: FZ-2122 (polyether modified polysiloxane, manufactured by Toray Dow Corning, 1% by weight PGMEA solution) D-1: Cyclopentanone (solvent)

[table 3] Example 9 Example 10 Comparative example 2 Comparative example 3 Polymerizable composition Polymerizable composition 1 Polymerizable composition 2 Comparative polymerizable composition 1 Comparative polymerizable composition 2 A-1 1.5 - - - A-2 - 1.5 - - A'-3 - - 1.5 - A'-4 - - - 1.5 B-1 23.6 23.6 23.6 23.6 B-2 14.8 14.8 14.8 14.8 C-1 7.3 7.3 7.3 7.3 D-1 52.8 52.8 52.8 52.8 total 100 100 100 100

[化24]

[Evaluation Examples 1 and 2 and Comparative Evaluation Examples 1 and 2] Regarding the cured products of polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2, the presence or absence of residual film was confirmed in the following order. The results are shown in Table 5. Using a spin coater (500 rpm × 2 seconds → 1000 rpm × 10 seconds → slope × 0.5 seconds), polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2 (approximately 2 mL coating amount) The film is coated on a glass substrate (10 cm×10 cm), and pre-baked (90° C.×90 seconds) in an oven to form a film. For each film, shield the step-type exposure meter (33-segment type, OD value 0～3, Table 4) with gray levels with continuous changes in transmittance, and use UV-LED (365 nm) to irradiate a specific amount of ultraviolet light (illuminance 20 mW/cm ² , exposure time 150 seconds, cumulative exposure 3000 mJ/cm ² ). After exposure, post-baking (100°C×20 minutes) in an oven, developing (PGMEA, 30 seconds) and washing (isopropanol, 10 seconds). With regard to the obtained cured film sample, visually confirm the remaining order. The so-called remaining order refers to the maximum order remaining in the cured film. Determine the transmittance according to the remaining order and according to Table 4, and calculate the conversion sensitivity by using the following formula. Conversion sensitivity (mJ/cm ² ) = Cumulative exposure (3000 mJ/cm ² )×Transmittance (%) Table 5 shows the remaining steps and conversion sensitivity.

[Table 4] Order 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 twenty one 2.04 0.912 twenty two 2.14 0.724 twenty three 2.24 0.575 twenty four 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] Evaluation example 1 Evaluation example 2 Comparative Evaluation Example 1 Comparative Evaluation Example 2 Polymerizable composition Polymerizable composition 1 Polymerizable composition 2 Comparative polymerizable composition 1 Comparative polymerizable composition 2 Remaining order [segment] 15 6 0 0 Conversion sensitivity [mJ/cm ² ] 109 865 ＞3000 ＞3000

According to the results of Table 5 above, the polymerizable composition containing the carbamethoxime compound of the present invention has more remaining stages (higher curability) than the comparative polymerizable composition, so the photobase generation efficiency is higher. It can be cured under low exposure and has high sensitivity to UV-LED light sources. Therefore, it is clear 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. [化25]

(Synthesis of oxime 8) Add 1,1'-(thiobis(4,1-phenylene))bis(hexane-1-one) 1.0 eq. to a 100 ml four-necked flask and dissolve it in dimethylformamide (400% by weight of theoretical output). Add 2.6 eq. of hydroxylammonium chloride and 2.6 eq. of pyridine to the solution. After the reaction mixture was heated and stirred at 55°C for 7 hours, ion-exchanged water was added, and extraction was performed with ethyl acetate. The organic layer was washed three times with ion-exchanged water, and dried and concentrated with magnesium sulfate. 1,2-Dichloroethane (12000% by weight of the theoretical output) was added to it to recrystallize, and the target product as a white powder was obtained with a yield of 77%.

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

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

[化26]

(Synthesis of Compound 10) Except that aniline was changed to 4-methylpiperidine, the same operation as in Example 11 was carried out to the water washing step. The concentrated residue was purified by silica gel column chromatography (eluent = ethyl acetate: toluene = 1:5), and the target compound was obtained as a light yellow viscous liquid compound with a yield of 80%. The obtained compound was subjected to ¹ H-NMR measurement. The results are shown in Table 7.

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

[化27]

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

(Synthesis of compound 11) The oxime body 1 was changed to the oxime body 9, and the aniline was changed to dibutylamine, respectively, and the same operation as in Example 11 was performed to the water washing step. The concentrated residue was purified by silica gel column chromatography (eluent = ethyl acetate: toluene = 1:20), and the target compound was obtained as a light yellow viscous liquid compound with a yield of 5%. The obtained compound was subjected to ¹ H-NMR measurement. The results are shown in Table 7.

[Table 6] Compound name Melting point (℃) Example 11 Compound 9 158 Example 12 Compound 10 (Liquid) Example 13 Compound 11 (Liquid)

[Table 7] Chemical shift/ppm (multiplicity, number of protons) Compound 9 (CDCl ₃ , 400 MHz) 8.31 (s, 2H), 7.65 (d, 4H), 7.50 (d, 4H), 7.44 (d, 4H), 7.35 (t, 4H), 7.12 (t, 2H), 2.93 (t, 4H), 1.65 -1.55 (m, 4H), 1.45-1.35 (m, 8H), 0.90 (t, 6H) Compound 10 (CDCl ₃ , 400 MHz) 7.67 (d, 4H), 7.33 (d, 4H), 4.35-4.05 (m, 4H), 3.00-2.70 (m, 8H), 1.70-1.50 (m, 10H), 1.40-1.25 (m, 8H), 1.25-1.10 (m, 4H), 0.96 (d, 6H), 0.89 (t, 6H) Compound 11 (CDCl ₃ , 400 MHz) 8.10 (d, 4H), 7.41 (d, 4H), 3.35-3.25 (m, 8H), 2.75 (t, 4H), 1.66-1.52 (m, 12H), 1.44-1.32 (m, 12H), 1.00- 0.90 (m, 18H) [Industrial availability]

The amine methyl oxime compound of the present invention has a higher photobase generation efficiency. When used as a polymerization initiator, it can generate bases more efficiently than the previous photobase generators. Therefore, it can be used even under low exposure. The polymerizable compound hardens. Especially when it is used in a curable resin composition containing an epoxy resin or a phenol resin, it exhibits high curability.

Claims (13)

A carboxime compound, which is represented by the following general formula (I), [化1]

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group,- OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a hydrocarbon group with 1 to 20 carbon atoms, a heterocyclic ring-containing group with 2 to 20 carbon atoms, and the methylene group in the hydrocarbon group is substituted to be selected from A group with 1 to 20 carbon atoms or a group represented by the following general formula (II) formed from a divalent group in the following <Group A>, R ¹¹ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, A heterocyclic group containing 2 to 20 carbon atoms or a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A> to form a group with 1 to 20 carbon atoms in the molecule When there are a plurality of R ¹¹ , they may be the same or different, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ It can also be the number of carbon atoms in which one or more of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ¹² , -COOR ¹² , -CO-R ¹² or -SR ¹² A group of 1 to 20, R ¹² represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, and the methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> with 1 carbon atom One or more of the hydrogen atoms in ～20 groups or hydrocarbon groups are substituted with halogen atoms, cyano groups, nitro groups, or hydroxyl groups, with 1 to 20 carbon atoms, and there are multiple R ^{12 in the molecule} In this case, they can be the same or different. <Group A> is -O-, ^{-CO-, -COO-, -NR 13} -, -NR ¹³ CO- and -S-, and R ¹³ represents a hydrogen atom Or a hydrocarbon group with 1 to 20 carbon atoms, when there are multiple R ¹³ in the molecule, they may be the same or different, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ can be independently connected to each other to form a hydrogen atom and a carbon atom with 3 to 10 carbon atoms Ring, one or more of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are groups represented by the following general formula (II), When there are multiple groups represented by the general formula (II) in the molecule, they may be the same or different groups) [化2]

(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B> ^{X 1 represents -NR 21} R ²² or the group represented by the following general formula (a) or the following general formula (b), R ²¹ and R ²² each independently represent A hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B> to form a group with 1 to 20 carbon atoms, R ²⁰ , R ²¹ and R ²² may also be one or more of the hydrogen atoms in the hydrocarbon group, which are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ R ²³ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, and the methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B> A group with 1 to 20 carbon atoms or one or more of the hydrogen atoms in a hydrocarbon group are substituted with halogen atoms, cyano groups, nitro groups, or hydroxyl groups. The groups have 1 to 20 carbon atoms. When there are a plurality of R ²³ , they may be the same or different. <Group B> is -O-, ^{-CO-, -COO-, -NR 24} -, -NR ²⁴ CO- and -S- , R ²⁴ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R ²⁴ in the group, they may be the same or different. R ²¹ and R ²² may be connected to each other to form a hydrogen atom , Nitrogen atom and carbon atom ring with 2 to 10 carbon atoms or ring containing hydrogen atom, oxygen atom, nitrogen atom and carbon atom with 2 to 10 carbon atoms, n represents 0 or 1, * represents a bonding bond) [化3]

(In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a hydrocarbon group The methylene group in is substituted with a group of 1 to 20 carbon atoms selected from the divalent group in the following <Group C>, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ may also be one or more of the hydrogen atoms in the hydrocarbyl group substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ⁴¹ , -COOR ⁴¹ ,- CO-R ⁴¹ or -SR ⁴¹ is a group with 1 to 20 carbon atoms. R ⁴¹ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R ⁴¹ in the group, they may be The same or different, <group C> is -O-, ^{-CO-, -COO-, -NR 42} -, -NR ⁴² CO- and -S-, R ⁴² represents a hydrogen atom or carbon number 1-20 When there are a plurality of R ⁴² in the base, they may be the same or different, R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ can be independently connected to each other to form a ring with 2-10 carbon atoms containing hydrogen, nitrogen and carbon atoms or 2-10 carbon atoms containing hydrogen, oxygen, nitrogen and carbon atoms The ring, * means bonding bond). The aminomethoxime compound of claim 1, wherein R ⁸ in the general formula (I) is the group represented by the above general formula (II). The carboxime compound of claim 2, wherein any one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ in the general formula (I) The above is -CO-R ¹¹ . The carboxime compound of claim 2, wherein any one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ in the general formula (I) The above is nitro. The aminomethoxime compound of claim 1, wherein R ³ and R ⁸ in the general formula (I) are the groups represented by the above general formula (II). The carbamate compound of claim 1, wherein X ¹ in the general formula (II) is -NR ²¹ R ²² , and R ²¹ and R ²² are connected to each other to form the number of carbon atoms including hydrogen, nitrogen and carbon atoms It is a ring of 2-10 or a ring of 2-10 carbon atoms including a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom. The amine carboxamide compound of claim 1, wherein X ¹ in the general formula (II) is -NR ²¹ R ²² , R ²¹ is a hydrogen atom, and R ²² is an aromatic hydrocarbon group with 6 to 20 carbon atoms or R ²¹ And R ²² are both aliphatic hydrocarbon groups having 1 to 20 carbon atoms. A potential alkali generator, which contains the carbamate compound according to any one of claims 1 to 7. A polymerization initiator containing the carboxamide oxime compound according to any one of claims 1 to 7. A polymerizable composition containing the carbamate compound and polymerizable compound according to any one of claims 1 to 7. The polymerizable composition of claim 10, wherein the polymerizable compound is an epoxy resin or an ethylenically unsaturated compound, or a mixture containing an epoxy resin and a phenol resin, a mixture containing an epoxy resin and a thiol compound, or A mixture of ethylenically unsaturated compounds and mercaptan compounds. A cured product, which is a cured product of the polymerizable composition of claim 10. A method for manufacturing a hardened product, which has a step of irradiating the polymerizable composition according to claim 10 with energy rays.