JP2020200272A - Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing the compound - Google Patents

Abstract

To provide a compound having high light base generation efficiency.SOLUTION: The present invention provides a carbamoyl oxime compound represented by formula (I) where R1-15 each denote a specific group.SELECTED DRAWING: None

Description

The present invention relates to carbamoyloxime compounds.

In general, a polymerizable composition such as a photosensitive resin composition is obtained by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and can be polymerized and cured or developed by irradiation with energy rays (light). Therefore, it is used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, and the like.

Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by energy ray (light) irradiation. The photoradical generator has advantages such as a high curing rate and no active species remaining after curing, but has a disadvantage that a layer or the like that blocks oxygen must be provided in the curing of the thin film because the curing is inhibited by oxygen. There is. The photoacid generator has an advantage that it is not inhibited by oxygen, but has a disadvantage that the residual active acid causes the metal substrate to be corroded and the cured resin to be modified. Photobase generators are attracting attention because they are less likely to cause problems such as inhibition of curing by oxygen and corrosion by residual active species, but generally have a problem of low sensitivity (low curability) as compared with photoacid generators. Photobase generators are described, for example, in Patent Documents 1 and 2.

International Publication No. 2013/141014 Japanese Unexamined Patent Publication No. 2013-163670

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

The present inventor conducted diligent studies and found that a compound having a specific structure has a high photobase generation efficiency and is useful as a polymerization initiator.
That is, the present invention is a carbamoyloxime compound represented by the following general formula (I).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、−ＯＲ^１６、−ＣＯＯＲ^１６、−ＣＯ−Ｒ^１６、−ＳＲ^１６、炭素原子数１〜２０の炭化水素基、炭素原子数２〜２０の複素環含有基、又は下記一般式（ＩＩ）で表される基を表し、
Ｒ^１６は、水素原子、炭素原子数１〜２０の炭化水素基又は炭素原子数２〜２０の複素環含有基を表し、分子中にＲ^１６が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基、水酸基、−ＯＲ^１７、−ＣＯＯＲ^１７、−ＣＯ−Ｒ^１７又は−ＳＲ^１７で置換された炭素原子数１〜２０の基であってもよく、
Ｒ^１７は、水素原子、炭素原子数１〜２０の炭化水素基、又は炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基又は水酸基で置換された炭素原子数１〜２０の基を表し、分子中にＲ^１７が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７は、炭化水素基中のメチレン基の１つ又は２つ以上が、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^１８−、−ＮＲ^１８ＣＯ−又は−Ｓ−で置換された炭素原子数１〜２０の基であってもよく、
Ｒ^１８は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、分子中にＲ^１８が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^４とＲ^５、Ｒ^６とＲ^７、Ｒ^７とＲ^８、Ｒ^８とＲ^９、Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２、Ｒ^１２とＲ^１３、Ｒ^１３とＲ^１４、及びＲ^１４とＲ^１５は、それぞれ独立に、互いに連結して、水素原子及び炭素原子からなる炭素原子数３〜１０の環を形成していてもよく、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５のうち、１つ以上は下記一般式（ＩＩ）で表される基であり、分子中に、一般式（ＩＩ）で表される基が複数存在する場合、それらは同一の基であっても異なる基であってもよい。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are Independently, hydrogen atom, halogen atom, cyano group, nitro group, -OR ¹⁶ , -COOR ¹⁶ , -CO-R ¹⁶ , -SR ¹⁶ , hydrocarbon group with 1 to 20 carbon atoms, 2 to 2 carbon atoms. Represents 20 heterocyclic-containing groups or groups represented by the following general formula (II).
R ¹⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms, and when a plurality of R ^16s are present in the molecule, they may be the same. May be different
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15 and ^{R 16} are carbonized Number of carbon atoms in which one or more hydrogen atoms in a hydrogen group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹⁷ , -COOR ¹⁷ , -CO-R ¹⁷ or -SR ^17. It may be a group of 1 to 20
R ¹⁷ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group. Represents a group with 1 to 20 atoms, and if there are multiple R ^{17s in} the molecule, they may be the same or different.
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16 and ^{R 17} is one or two or more methylene groups in the hydrocarbon group, -O -, - CO -, - COO -, - OCO -, - NR 18 -, - NR 18 CO- or -S- substituted It may be a group having 1 to 20 carbon atoms.
R ¹⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^18s are present 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, R 11} And R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ are independently connected to each other to form a ring consisting of hydrogen and carbon atoms with 3 to 10 carbon atoms. You may be
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, of ^{R 14} and ^{R 15,} 1 or more Is a group represented by the following general formula (II), and when there are a plurality of groups represented by the general formula (II) in the molecule, they may be the same group or different groups. Good. )

（式中、Ｒ^２０は、水素原子、ハロゲン原子、ニトロ基、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、
Ｘ^１は、−ＮＲ^２１Ｒ^２２、又は下記一般式（ａ）若しくは下記一般式（ｂ）で表される基を表し、
Ｒ^２１及びＲ^２２は、それぞれ独立に、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
Ｒ^２０、Ｒ^２１及びＲ^２２は、炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基、水酸基、−ＯＲ^２３、−ＣＯＯＲ^２３、−ＣＯ−Ｒ^２３又は−ＳＲ^２３で置換された炭素原子数１〜２０の基であってもよく、
Ｒ^２３は、水素原子、炭素原子数１〜２０の炭化水素基、又は炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基又は水酸基で置換された炭素原子数１〜２０の基を表し、基中にＲ^２３が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^２０、Ｒ^２１、Ｒ^２２及びＲ^２３は、炭化水素基中のメチレン基の１つ又は２つ以上が、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^２４−、−ＮＲ^２４ＣＯ−又は−Ｓ−で置換された炭素原子数１〜２０の基であってもよく、
Ｒ^２４は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、基中にＲ^２４が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^２１とＲ^２２は、互いに連結して、水素原子、窒素原子及び炭素原子からなる炭素原子数２〜１０の環、又は水素原子、酸素原子、窒素原子及び炭素原子からなる炭素原子数２〜１０の環を形成していてもよく、
ｎは、０又は１を表し、
＊は結合手を表す。）

(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms.
X ¹ represents −NR ²¹ R ²² or a 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 or a hydrocarbon group having 1 to 20 carbon atoms.
In R ²⁰ , R ²¹ and R ²² , one or more of the hydrogen atoms in the hydrocarbon group are halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ²³ , -COOR ²³ , -CO-R ^23. Alternatively, it may be a group having 1 to 20 carbon atoms substituted with −SR ²³ .
R ²³ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group. It represents a group with 1 to 20 atoms, and when a plurality of R ^23s are present in the group, they may be the same or different.
In R ²⁰ , R ²¹ , R ²² and R ²³ , one or more of the methylene groups in the hydrocarbon group are -O-, -CO-, -COO-, -OCO-, -NR ^24- , It may be a group having 1 to 20 carbon atoms substituted with −NR ²⁴ CO− or −S−.
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ²⁴ are present in the group, they may be the same or different.
R ²¹ and R ²² are connected to each other and have a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom. It may form 10 rings,
n represents 0 or 1 and represents
* Represents a bond. )

（式中、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９及びＲ^４０は、それぞれ独立に、水素原子、炭素原子数１〜２０の炭化水素基を表し、
Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９及びＲ^４０は、炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基、水酸基、−ＯＲ^４１、−ＣＯＯＲ^４１、−ＣＯ−Ｒ^４１又は−ＳＲ^４１で置換された炭素原子数１〜２０の基であってもよく、
Ｒ^４１は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、基中にＲ^４１が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９及びＲ^４０は、炭化水素基中のメチレン基の１つ又は２つ以上が、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^４２−、−ＮＲ^４２ＣＯ−又は−Ｓ−で置換された炭素原子数１〜２０の基であってもよく、
Ｒ^４２は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、基中にＲ^４２が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^３１とＲ^３２、Ｒ^３３とＲ^３４、Ｒ^３５とＲ^３６、Ｒ^３７とＲ^３８、及びＲ^３９とＲ^４０は、それぞれ独立に、互いに連結して、水素原子、窒素原子及び炭素原子からなる炭素原子数２〜１０の環、又は水素原子、酸素原子、窒素原子及び炭素原子からなる炭素原子数２〜１０の環を形成していてもよく、
＊は結合手を表す。）

(In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are independently carbonized with a hydrogen atom and 1 to 20 carbon atoms, respectively. Represents a hydrogen group
In R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ , one or more of the hydrogen atoms in the hydrocarbon group are halogen atoms. It may be a group having 1 to 20 carbon atoms substituted with a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ .
R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^41s are present in the group, they may be the same or different.
In R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ , one or more of the methylene groups in the hydrocarbon group are -O-. , -CO -, - COO -, - OCO -, - NR 42 -, - NR 42 CO- or -S- in may be a substituted group having 1 to 20 carbon atoms,
R ⁴² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^42s are present in the group, they may be the same or different.
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ are independently linked to each other and are derived from hydrogen, nitrogen and carbon atoms, respectively. It may form a ring having 2 to 10 carbon atoms, or a ring having 2 to 10 carbon atoms composed of hydrogen atom, oxygen atom, nitrogen atom and carbon atom.
* Represents a bond. )

The carbamoyloxime compound of the present invention has a high photobase generation efficiency, and when used as a polymerization initiator, it can generate a base more efficiently than a conventional photobase generator, so that the exposure amount is low. Also, the polymerizable compound can be cured. In particular, when used in a curable resin composition containing an epoxy resin or a phenol resin, it exhibits high curability.

Hereinafter, the present invention will be described in detail.
The carbamoyloxime compound of the present invention is represented by the above general formula (I). The carbamoyl oxime compound represented by the general formula (I) has geometric isomers due to a double bond of oxime, but these are not distinguished.
That is, in the present specification, the carbamoyloxime compound represented by the above general formula (I), and the compound which is a preferable form of the compound described later and the exemplified compound represent a mixture of isomers or one of them. It is not limited to the isomer of the structure shown.
Hereinafter, the carbamoyloxime compound represented by the general formula (I) is also simply referred to as "a compound represented by the general formula (I)" or "a 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.

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

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

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

One or more of the hydrogen atoms in the hydrocarbon group represented by R ^{1 to} R ¹⁶ are halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ¹⁷ , -COOR ¹⁷ , -CO-R ^17. Alternatively, as the group having 1 to 20 carbon atoms substituted with −SR ¹⁷ , one or two or more hydrogen atoms in the above hydrocarbon groups having 1 to 20 carbon atoms are halogen atoms, cyano groups, and nitro groups. , Hydrocarbon, -OR ¹⁷ , -COOR ¹⁷ , -CO-R ¹⁷ or -SR ¹⁷ , and the total number of carbon atoms is 1 to 20. Further, as a group having 1 to 20 carbon atoms in which one or two or more hydrogen atoms in the hydrocarbon group represented by R ¹⁷ are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, One or two or more of the hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group, and the total number of carbon atoms is 1 to 20. There is a group that is.

Represented by R ¹ to R ^17, one of the methylene groups in the hydrocarbon group or two or more, -O -, - CO -, - COO -, - OCO -, - NR 18 -, - NR 18 As the group having 1 to 20 carbon atoms substituted with CO- or -S-, one or two or more methylene groups in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms are -O-,-. CO -, - COO -, - OCO -, - NR 18 -, - NR 18 CO- , or -S- in a structure substituted include groups total number of carbon atoms is 1 to 20.

One or more of the hydrogen atoms in the hydrocarbon group represented by R ^{20 to} R ²² are halogen atom, cyano group, nitro group, hydroxyl group, -OR ²³ , -COOR ²³ , -CO-R ^23. Alternatively, as the group having 1 to 20 carbon atoms substituted with −SR ²³ , one or two or more hydrogen atoms in the above hydrocarbon groups having 1 to 20 carbon atoms are halogen atoms, cyano groups, or nitro groups. , Hydrocarbon, -OR ²³ , -COOR ²³ , -CO-R ²³ or -SR ²³ , and the total number of carbon atoms is 1 to 20. Further, as a group having 1 to 20 carbon atoms in which one or two or more hydrogen atoms in the hydrocarbon group represented by R ²³ are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, One or two or more of the hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group, and the total number of carbon atoms is 1 to 20. There is a group that is.

One or more of the methylene groups in the hydrocarbon groups represented by R ^{20 to} R ²³ are -O-, -CO-, -COO-, -OCO-, -NR ^24- , -NR ^24. As the group having 1 to 20 carbon atoms substituted with CO- or -S-, one or two or more methylene groups in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms are -O-,-. Examples thereof include groups having a structure substituted with CO-, -COO-, -OCO-, -NR ^24- , -NR ²⁴ CO- or -S-, and having a total carbon atom number of 1 to 20.

One or more of the hydrogen atoms in the hydrocarbon group represented by R ^{31 to} R ⁴⁰ are halogen atom, cyano group, nitro group, hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ^41. Alternatively, as the group having 1 to 20 carbon atoms substituted with −SR ⁴¹ , one or two or more hydrogen atoms in the above hydrocarbon groups having 1 to 20 carbon atoms are halogen atoms, cyano groups, or nitro groups. , Hydrocarbon, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ , and the total number of carbon atoms is 1 to 20.

Represented by R ³¹ to R ^40, one of the methylene groups in the hydrocarbon group or two or more, -O -, - CO -, - COO -, - OCO -, - NR 42 -, - NR 42 As the group having 1 to 20 carbon atoms substituted with CO- or -S-, one or two or more methylene groups in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms are -O-,-. CO -, - COO -, - OCO -, - NR 42 -, - NR 42 CO- , or -S- in a structure substituted include groups total number of carbon atoms is 1 to 20.

Examples of the heterocyclic group having 2 to 20 carbon atoms in the general formula (I) include a tetrahydrofuranyl group, a dioxolanyl group, a tetrahydropyranyl group, a morpholic group, a furanyl group, a thiophenyl group, a methylthiophenyl group and a hexylthio. Examples thereof include a phenyl group, a benzothiophenyl group, a pyrrolyl group, a pyrrolidinyl group, an imidazolyl group, an imidazolinyl group, an imidazolidinyl group, a pyrazolinyl group, a pyrazoridinyl group, a piperidinyl group and a group containing a piperazinyl group.

The heterocyclic group having 2 to 20 carbon atoms has a halogen atom, a cyano group, a nitro group, a hydroxyl group, a substituent such as −OR ⁵⁰ , −COOR ⁵⁰ , −CO-R ⁵⁰ or −SR ^50. even if well, -O -, - CO -, - COO -, - OCO -, - NR 51 -, - NR 51 CO- or -S- like structure may include a.
Here, R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁵⁰ and R ⁵¹ are carbons in the general formula (I), the general formula (II), the general formula (a), and the general formula (b). It is the same as the hydrocarbon group having 1 to 20 atoms.

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 in the above general formula (I). ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ are connected to each other to form 3 to 10 carbon atoms consisting of hydrogen and carbon atoms. Examples of the ring include a benzene ring, a cyclohexene ring, a cyclohexane ring, a cyclopentadiene ring, a cyclopentane ring and the like. Further, these rings may have a substituent, and examples of the substituent include a substituent which may be contained by the heterocyclic ring-containing group having 2 to 20 carbon atoms.

R ²¹ and R ²² , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ^{38 in the} general formula (II), the general formula (a) and the general formula (b). , And R ³⁹ and R ⁴⁰ are connected to each other, and the ring consisting of hydrogen atom, nitrogen atom and carbon atom having 2 to 10 carbon atoms is a pyrrol ring as a ring including the bonded nitrogen atom. , Pyrrolidine ring, imidazole ring, imidazolidine ring, imidazoline ring, pyrazole ring, pyrazolidine ring, piperidine ring, piperazine ring and the like. These rings may have a substituent, and examples of the substituent include a substituent that may be contained in the heterocyclic ring-containing group having 2 to 20 carbon atoms.

R ²¹ and R ²² , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ^{38 in the} general formula (II), the general formula (a) and the general formula (b). As a ring having 2 to 10 carbon atoms composed of hydrogen atom, oxygen atom, nitrogen atom and carbon atom formed by connecting R ³⁹ and R ⁴⁰ with each other, as a ring including a bonded nitrogen atom. , Morphorine ring, oxazoline ring, oxazoline ring, oxadiazole ring and the like. These rings may have a substituent, and examples of the substituent include a substituent that may be contained in the heterocyclic ring-containing group having 2 to 20 carbon atoms.

In the present invention, since the compound is easy to synthesize, the storage stability is high, and the base generation efficiency is high, one or more of R ³ , R ⁸ and R ^{13 in} the general formula (I) are described above. The group represented by the general formula (II) is preferable, and one of R ³ , R ⁸ and R ¹³ is more preferably a group represented by the general formula (II).

^R 1 in the general formula ^{(I), R 2, R} 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14 and R Of ¹⁵ , it is preferable that one or more is −CO-R ¹⁶ because it cures at a low exposure amount. In particular, it is preferable that one or more of R ³ , R ⁸ and R ¹³ is −CO-R ¹⁶ because the compound can be easily synthesized and the storage stability is high. In this case, it is preferable that R ¹⁶ is an aromatic hydrocarbon group having 6 to 20 carbon atoms because it cures at a low exposure amount, and in particular, an aromatic hydrocarbon containing a benzene ring having 6 to 10 carbon atoms. Groups are preferred.

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 a ring or hydrogen having 2 to 10 carbon atoms consisting of hydrogen atom, nitrogen atom and carbon atom. It is preferable to form a ring having 2 to 10 carbon atoms composed of an atom, an oxygen atom, a nitrogen atom and a carbon atom because of high base generation efficiency, and it is preferable to form a ring having 2 to 10 carbon atoms composed of hydrogen atom, nitrogen atom and carbon atom. A ring of ~ 6 or a ring of 2 to 6 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom is more preferable.
In particular, it is preferable that R ²¹ and R ²² are connected to each other to form a ring having 2 to 6 carbon atoms composed of a hydrogen atom, a nitrogen atom and a carbon atom, and form a piperidine ring or a pyrrolidine ring. It is more preferable to have.

The compound in which n in the general formula (II) is 0 is preferable because it has high heat stability.
The compound in which n in the general formula (II) is 1 is preferable because it cures at a low exposure amount.

Most preferably in the present invention, R ³ in the general formula (I) is a group represented by the above general formula (II), and X ¹ in the general formula (II) is −NR ²¹ R ²² . R ²¹ and R ²² are connected to each other to form a ring consisting of hydrogen atom, nitrogen atom and carbon atom having 2 to 10 carbon atoms, R ¹³ is −CO-R ¹⁶ and R ¹⁶ is a carbon atom. It is a carbamoyloxime compound having a number of aromatic hydrocarbon groups of 6 to 20 and n being 0.

Specific examples of the carbamoyloxime compound represented by the general formula (I) include compounds represented by the following chemical formulas (1) to (80). However, the present invention is not limited by the following compounds.

In group manufacturing method of the carbamoyl oxime compound of the present invention represented by the aforementioned general formula (I) is not particularly limited, for example, the general formula (I) R ³ in is represented by the general formula (II) If X ¹ is −NR ²¹ R ²² and n = 0, it can be produced by the following method according to the following reaction formula 1.
That is, an oxime compound is obtained by reacting a known ketone compound with hydroxylamine hydrochloride in the presence of a base such as pyridine. Subsequently, the oxime compound is reacted with 4-nitrophenyl chloroformate and then with an amine to obtain the carbamoyl oxime compound of the present invention.

（式中、Ｒ^１〜Ｒ^１５、Ｒ^２０〜Ｒ^２２は、上記一般式（Ｉ）と同じである。）

(In the formula, R ^{1 to} R ¹⁵ and R ^{20 to} 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, X ¹ is represented by the above general formula (a) or the above general formula (b). The base compound can also be produced.
Further, the above reaction formula 1 shows a case where R ³ in the general formula (I) is a group represented by the general formula (II), but a ketone group is introduced at an arbitrary position other than R ^3. By using the obtained ketone compound as a raw material, a compound in which a group represented by the general formula (II) is introduced at a position other than R ³ can also be obtained.
The oxime compound can also be produced by the method described in Japanese Patent No. 4223071.

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

The latent base generator of the present invention means a composition containing a compound having a function of efficiently generating a base by irradiating with light such as ultraviolet rays, and its use is as a pH adjuster. Examples include a catalyst using a base.

Further, the carbamoyloxime compound of the present invention is useful as a photobase generator and a photoradical polymerization initiator because of its high efficiency of generating bases and radicals by light irradiation among the above-mentioned polymerization initiators, and has a high base generation efficiency. Since it is very expensive, it is particularly useful as a photobase generator.

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

The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass because of the high base generation efficiency.

The polymerizable composition of the present invention contains a polymerization initiator (A) containing at least one carbamoyloxime compound represented by the above general formula (I), and a polymerizable compound (B).
The content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound (B). When the content of the polymerization initiator (A) is 1 part by mass or more, it is easy to prevent curing failure due to insufficient curing sensitivity. Therefore, when it is 20 parts by mass or less, it volatilizes during light irradiation or heating. It is preferable because it can suppress objects.

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 a base is added, and a radically polymerizable compound. A photosensitive resin that polymerizes and cures by irradiating with energy rays such as ultraviolet rays or a cured resin that lowers the curing temperature is preferable. The anion-polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by an active energy ray such as ultraviolet rays, and for example, an epoxy group, an episulfide group, or a cyclic monomer (σ-valerolactone, Ε-Caprolactam), malonic acid ester and the like. Reactions in which a base acts as a catalyst or a base is added include a urethane bond formation reaction between isocyanate and alcohol, an addition reaction between an epoxy resin and a compound containing a hydroxyl group, and an addition reaction between an epoxy resin and a compound containing a carboxylic acid group. , Addition reaction of epoxy resin and thiol compound, Michael addition reaction of (meth) acrylic group, dehydration condensation reaction of polyamic acid, hydrolysis / polycondensation reaction of alkoxysilane and the like.

Examples of the compound having an anionic polymerizable functional group include epoxy resin, oxetane resin, episulfide resin, cyclic amide (lactam compound), cyclic ester (lactone compound), cyclic carbonate compound, malonic acid ester and the like. Examples of compounds that are cured by a reaction in which a base acts as a catalyst or a reaction in which a base is added include a polyamide resin (polynitation reaction by dehydration cyclization), an epoxy / hydroxyl group (ring-opening addition reaction), and an epoxy / carboxylic acid system. (Ring-opening addition reaction), epoxy-thiol-based (ring-opening addition reaction), epoxy-acid anhydride-based (ring-opening polycondensation), cyanate ester (cyclization reaction), cyanate ester-epoxy-based (cyclization reaction), Cyanate ester (cyclization reaction), cyanate ester / maleimide system (bridge copolymerization), oxetane / hydroxyl group system (ring opening addition reaction), oxetane / carboxylic acid system (ring opening addition reaction), oxetane / thiol system (ring opening addition reaction) Reaction), oxetane / acid anhydride system (ring-opening polycondensation), episulfide / hydroxyl group (ring-opening addition reaction), episulfide-carboxylic acid system (ring-opening addition reaction), episulfide-thiol system (ring-opening addition reaction), Episulfide / acid anhydride type (ring-opening polycondensation) acrylic thiol type (Michael addition reaction), methacryl-thiol type (Michael addition reaction), acrylic amine type (Michael addition reaction), methacryl amine type (Michael addition reaction) ), Carous acid / hydroxyl type (polyesterization reaction), carboxylic acid / amine type (polyamide formation reaction), isocyanate / hydroxyl type (polyurization reaction), alkoxysilane type (hydrolysis / polycondensation) and the like. Examples of the compound polymerized by radicals include ethylenically unsaturated compounds. Since it has high 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. As a preferable combination, a combination of an epoxy resin and a phenol resin is excellent in that the reaction proceeds quickly and the adhesiveness is good, and a combination of an epoxy resin and a thiol compound and a high reactivity because of excellent low-temperature curability. Therefore, a combination of an ethylenically unsaturated compound and a thiol compound can be mentioned.

Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and fluorocurxinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), and methylenebis (orthocresol). , Etiriden bisphenol, isopropyridene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropyridenebis (orthocresol), 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, oxy Polyglycidyl ether compounds of polynuclear polyvalent phenolic compounds such as bisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac, terpenphenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, poly Polyglycidyl ethers of polyhydric alcohols such as glycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberin Acids, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acids, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N) -Glysidylamino) phenyl) methane, diglycidyl orthotoluidine and other epoxy compounds with glycidylamino groups; vinylcyclohexene diepoxide, dicyclopentanediene diepoxiside, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate , 3,4-Epoxy-6-methylcyclo Epoxides of cyclic olefin compounds such as hexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, epoxidized styrene Examples include epoxidized conjugated diene polymers such as butadiene copolymers and heterocyclic compounds such as triglycidyl isocyanurate. Further, these epoxy resins may be those internally crosslinked by a prepolymer of terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). ..
Among the above epoxy resins, those having a glycidyl group are preferable, and those having a bifunctional or higher functional glycidyl group are more preferable, from the viewpoint of excellent curability.

As the phenol resin, a phenol resin having two or more hydroxy groups in one molecule is preferable, and generally known ones can be used. Examples of the phenol resin include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, and aralkyl novolac. Type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol Resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin, and hydroxyl group-containing Examples thereof include silicone resins, but the present invention is not particularly limited. These phenolic resins may be used alone or in combination of two or more.

The thiol compound is not particularly limited and includes all thiol compounds, but those having two or more thiol groups in one molecule are preferable.
Preferred specific examples of the thiol compound are bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-ditian, 1,3-bis (mercaptomethyl) benzene, and 1,4-bis (mercapto). Methyl) benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Mercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecan, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecan, 1,2,6,7 -Tetramercapto-4-thiaheptan, pentaerythrithiol, 1,1,3,3-tetrakis (mercaptomethylthio) propane, pentaerythritol tetrakis mercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropanthithioglycolate , And trimethylolpropanthris mercaptopropionate, more preferably 1,2,6,7-tetramercapto-4-thiaheptan, pentaerythrithiol, bis (2-mercaptoethyl) sulfide, 2,5-. Bis (2-mercaptomethyl) -1,4-dithian, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,3-bis (mercaptomethyl) benzene, pentaerythritol tetrakis mercaptopropionate, And pentaerythritol tetraxthioglycolate.
Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptan, pentaerythrithiol, bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4 -Mercaptomethyl-1,8-dimercapto-3,6-dithiane octane.
The thiol compound may be used alone or in combination of two or more.

The polyamide resin includes ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride as acid dianhydride. , 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Etc. as diamines, (o-, m- or p-) phenylenediamine, (3,3'-or 4,4'-) diaminodiphenyl ether, diaminobenzophenonone, (3,3'-or 4,4' -) Examples thereof include resins made from diaminodiphenylmethane or the like.

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

Examples of the ethylenically unsaturated compound include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid and α-chloro. Acrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloy Roxyethyl], mono (2- (meth) acrylicyloxyethyl] phthalate, ω-carboxypolycaprolactone mono (meth) acrylate, etc. Polymer mono (meth) acrylate having carboxy groups and hydroxyl groups at both ends; hydroxy Unables such as ethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups. Saturated polybasic acid; -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following acrylic compound No. 1-No. 4. Methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, Aminopropyl (Meta) Acrylate, Dimethylaminopropyl (Meta) Acrylate, ethoxyethyl (Meta) Acrylate, Poly (ethoxy) Ethyl (Meta) Acrylate, Butoxyethoxyethyl (Meta) Acrylate, (Meta) ) Ethylhexyl acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanthry (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, Unsaturated monobasic acids such as pentaerythritol tri (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomer, and polyhydric alcohols or polyvalents. Esters of phenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate, magnesium (meth) acrylate; maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, methyltetrahydrophthalic anhydride, tetrahydro Acrylate, TrialkyltetrahydroAcrylate, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthaliclate-male anhydride Acid anhydrides of unsaturated polybasic acids such as phosphate adducts, dodecenyl anhydride succinic acid, methylhymic anhydride; (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) Amid of unsaturated monobasic acids and polyvalent amines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as achlorine; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol , Vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether and other unsaturated aromatic compounds; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidin and the like. Unsaturated amine compounds; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; maleimide, N-phenylmaleimide, N-cyclohexyl Unsaturated imides such as maleimide; indens such as inden and 1-methylinden; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n-butyl ( Macromonomonics having a mono (meth) acryloyl group at the end of a polymer molecular chain such as a meta) acrylate or polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isothia Examples thereof include vinyl urethane compounds of nurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound, and vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound.
The ethylenically unsaturated compound can be used alone or in combination of two or more.

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

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

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

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

Examples of the coloring material include pigments, dyes, and natural pigments. These coloring materials can be used alone or in combination of two or more.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antanthurone compounds; perinone. Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; azo dyes, cyanine dye metal complex compounds; lake pigments; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin, the above carbon black is previously dispersed in a solvent with a resin, and 20 A compound in which a resin of ~ 200 mg / g is adsorbed, a compound in which the above carbon black is subjected to an acidic or alkaline surface treatment, a carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, in a volatile matter at 950 ° C. Carbon black in which the total amount of oxygen calculated from CO and CO ₂ is 9 mg or more per 100 m ^{2 of} the surface area; graphite, graphite carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; Aniline Black, Pigment Black 7, Titanium Black; Chromium Oxide Green, Milori Blue, Cobalt Green, Cobalt Blue, Manganese, Ferocyanide, Phosphate Ultramarine, Navy Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate, Organic or inorganic pigments such as yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, and amber can be used. These pigments can be used alone or in combination of two or more.

As the pigment, a commercially available pigment may 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 Examples thereof include 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50.

Examples of the above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acrydin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes. , Dyes such as cyanine dyes, and the like, and a plurality of these may be mixed and used.

Examples of the latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenylsulfone, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas and melamines. Can be mentioned.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thioapple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-[N-( 2-Mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutansulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-Mercaptoethylamine, 2-Mercaptoimidazole, 2-Mercaptobenzoimidazole, 2-Mercapto-3-pyridinol, 2-Mercaptobenzothiazole, Mercaptoacetic acid, Trimethylolpropanthris (3-mercaptopropionate), Pentaerythritoltetrakis A mercapto compound such as (3-mercaptopropionate), a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid. Alkyliodated compounds such as, trimethylolpropanetris (3-mercaptoisobutyrate), butanediolbis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthio. Propionate, Butanediol Bisthioglycolate, Ethethylene Glycol Bisthioglycolate, Trimethylol Propanetristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, and Karenz MT BD1, PE1, NR1 manufactured by Showa Denko KK.

The solvent is usually a solvent capable of dissolving or dispersing each of the above components (polymerization initiator (A), polymerizable compound (B), etc.), for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl. Ketones such as ketone, methylisobutylketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate , Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol and other ester solvents; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate, Ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane Solvents: Terpen-based hydrocarbon oils such as terepine oil, D-lymonen, and pinen; mineral spirits, paraffin solvents such as Swazole # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvent such as carbon chloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol solvent; aniline; triethylamine; pyridine; acetic acid Acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide; water and the like can be used, and these solvents may be used alone or in admixture of two or more. It can be used as a solvent.
Among these, ketones or ether ester-based solvents, particularly propylene glycol-1-monomethyl ether-2-acetate (hereinafter, also referred to as "PGMEA") from the viewpoint of alkali developability, patterning property, film forming property, and solubility. ) Or cyclohexanone is preferably used.
In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, each component is uniformly dispersed or dissolved, and the polymerizable composition of the present invention exhibits a liquid or paste suitable for each application. Although it may be an amount, it is usually preferable to contain the solvent in a range in which the amount of the solid content (all components other than the solvent) in the polymerizable composition of the present invention is 10 to 90% by mass.

In addition, the polymerizable composition of the present invention can also improve the characteristics of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmethacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples thereof include polyester, phenol resin, and phenoxy resin.
When the above organic polymer is used, its content is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).

Further, a surfactant, a silane coupling agent, a melamine compound and the like can be used in combination with the polymerizable composition of the present invention.

Examples of the surfactant include fluorine-based surfactants such as perfluoroalkyl phosphate and perfluoroalkyl carboxylate; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher grades. Cationic surfactants such as amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; amphoteric surfactants; silicone-based surfactants Surfactants such as activators can be used, and these may be used in combination.

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

Examples of the melamine compound include all or a part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycol uryl, (poly) methylolbenzoguanamine, and (poly) methylol urea. Examples thereof include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be the same as each other or different from each other. Further, the methylol group which has not been alkyl etherized may be self-condensed in one molecule, or may be condensed between two molecules to form an oligomer component as a result.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycol uryl, tetrabutoxymethyl glycol uryl and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable from the viewpoint of solubility in a solvent and difficulty in crystal precipitation from the polymerizable composition.

In the polymerizable composition of the present invention, the content of optional components (excluding inorganic compounds, coloring materials, and solvents) other than the polymerization initiator (A) and the polymerizable compound (B) depends on the purpose of use thereof. It is appropriately selected and is not particularly limited, but 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 made into a cured product by irradiating it with energy rays. The cured product is formed into an appropriate shape according to the application. For example, when forming a film-like cured product, the polymerizable composition of the present invention is a soda by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion. It can be applied on a supporting substrate such as glass, quartz glass, a semiconductor substrate, metal, paper, or plastic. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

As the light source of the energy ray used for curing the polymerizable composition of the present invention, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, and a carbon arc High-energy rays such as electromagnetic energy and electron beam, X-ray, radiation, etc. having a wavelength of 2000 angstrom to 7000 angstrom obtained from lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, sterilization lamps, light emitting diodes, CRT light sources, etc. However, preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, or the like that emits light having a wavelength of 300 to 450 nm is used.

Furthermore, by using laser light as the exposure light source, the laser direct drawing method, which forms an image directly from digital information of a computer or the like without using a mask, improves not only productivity but also resolution and position accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, and a krypton ion laser are used. , Various semiconductor lasers, YAG lasers and the like that emit light in the visible to infrared region can also be used. When these laser beams are used, a sensitizing dye that absorbs the visible to infrared region is preferably added.

Further, in order to cure the polymerizable composition of the present invention, it is usually necessary to heat after irradiation with the above energy rays, and heating at about 40 to 150 ° C. is preferable in terms of the curing rate.

The polymerizable composition of the present invention is a photocurable paint or varnish; a photocurable adhesive; a coating agent for metals; a printed circuit board; a color display liquid crystal display element for a color television, a PC monitor, a mobile information terminal, a digital camera, or the like. Color filter in; CCD image sensor color filter; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photoresist for electronic engineering; Electroplated resist; Etching Resists; Dry films; Solder resists; Resists for manufacturing color filters for various display applications or for forming their structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; Electrical and electronic Composition for encapsulating parts; solder resist; magnetic recording material; micromechanical parts; waveguide; optical switch; plating mask; etching mask; color test system; glass fiber cable coating; screen printing stencil; stereolithography Materials for manufacturing three-dimensional objects by; Holography recording materials; Image recording materials; Microelectronic circuits; Decolorizing materials; Decolorizing materials for image recording materials; Decolorizing materials for image recording materials using microcapsules; Printing Photoresist material for wiring boards; Photoresist material for UV and visible laser direct imaging systems; Photoresist material used for forming dielectric layers in sequential lamination of printed circuit boards, or protective film, etc. It can be used, and its use is not particularly limited.

The polymerizable composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertically oriented liquid crystal display element. In particular, it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for a vertically oriented liquid crystal display element.

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

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

When used for the partition wall for an inkjet color filter, the partition wall formed from the polymerizable composition of the present invention partitions on the transferred body, and droplets are applied to the recesses on the partitioned partition by the inkjet method. The optical element is manufactured by the method of forming an image region. At this time, it is preferable that the droplets contain a colorant and the image region is colored. In that case, the optical element manufactured by the above manufacturing method is formed from a plurality of colored regions on the substrate. It has at least a partition wall that separates the pixel group and each colored region of the pixel group.

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

The insulating film is used for the insulating resin layer in a laminated body in which an insulating resin layer is provided on a peelable supporting base material, and the laminated body can be developed with an alkaline aqueous solution and is an insulating resin layer. The thickness of the film is preferably 10 to 100 μm.

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

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

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

(Synthesis of oxime body 1)
In a 100 ml four-necked flask, 1-(4-((4- (2-methylbenzoyl) phenyl) (phenyl) amino) phenyl) ethane-1-one 1.0 eq. Was added and dissolved in ethyl acetate (600% by mass of theoretical yield). Hydroxylamine hydrochloride 1.5 eq. And pyridine 3.0 eq. Was added, and the mixture was heated under reflux for 5 hours. The reaction solution was washed with 5% by mass hydrochloric acid, ion-exchanged water, and saturated aqueous sodium hydrogen carbonate solution in this order, and then washed with ion-exchanged water three more times to neutralize the reaction solution. The organic layer was dried over magnesium sulfate, concentrated, and methanol (500% by weight) was added to the residue for crystallization to obtain oxime 1 in a yield of 83%.

(Synthesis of Compound 1)
In a 100 ml four-necked flask, 1.0 eq. , Dichloromethane (600% by weight of theoretical yield), triethylamine 3.0eq. Was added, and the mixture was stirred on an ice bath at 5 ° C. There, 4-nitrophenyl chloroformate 1.1eq. Was dissolved in dichloromethane and added dropwise. After completion of the dropping, the mixture was cooled to 5 ° C. in an ice bath, and piperidine 1.1 eq. Was added dropwise. The mixture was stirred at room temperature for 1.5 hours and the solvent was evaporated under reduced pressure. The residue after concentration was purified by silica gel column chromatography (eluent = ethyl acetate: hexane = 1: 4 → 2: 1). This was dissolved in ethyl acetate, washed twice with a 1 mass% NaOH aqueous solution, and then washed with ion-exchanged water three more times. The organic layer was dried over magnesium sulfate and concentrated to obtain Compound 1 as a pale yellow powdery compound in a yield of 45%. ^{1 1} H-NMR measurement results are shown in Table 1.

[Example 2 and Comparative Example 1] Preparation of polymerizable composition The formulation shown in Table 2 was carried out to obtain a polymerizable composition 1 and a comparative polymerizable composition 1. The compounding values in the table indicate parts by mass.
The reference numerals of the respective components in the table represent the following components.
A-1: Compound 1
A'-2: Comparative compound 1
B-1: EPPN-201 (phenol novolac type epoxy resin, epoxy equivalent 193 g / eq., Manufactured by Nippon Kayaku Co., Ltd.)
B-2: H-3M (phenolic resin, hydroxyl group equivalent 105-109 g / eq., Manufactured by Meiwa Kasei Co., Ltd.)
C-1: FZ-2122 (polyether-modified polysiloxane, manufactured by Toray Dow Corning, 1 wt% PGMEA solution)
D-1: Cyclopentanone (solvent)

[Evaluation Example 1 and Comparative Evaluation Example 1]
With respect to the cured products of the polymerizable composition 1 and the comparative polymerizable composition 1, the presence or absence of a residual film was confirmed by the following procedure. The results are shown in Table 4.
The polymerizable composition 1 and the comparative polymerizable composition 1 are each applied to a glass substrate (10 cm × 10 cm) using a spin coater (500 rpm × 2 seconds → 1000 rpm × 10 seconds → slope × 0.5 seconds). A volume of about 2 mL) was prebaked in an oven (90 ° C. × 90 seconds) to form a film.
For each film, a step tablet (33-stage type, OD value 0 to 3, Table 3) having a gradation in which the transmittance changes continuously is masked, and UV-LED (365 nm) is used to expose ultraviolet light. A fixed amount of irradiation was performed (illuminance 20 mW / cm ² , exposure time 150 seconds, integrated exposure 3000 mJ / cm ² ).
After the exposure, it was post-baked (100 ° C. × 20 minutes) in an oven, developed (PGMEA, 30 seconds) and rinsed (isopropyl alcohol, 10 seconds).
The number of remaining stages of the obtained cured film sample was visually confirmed. The number of remaining stages means the maximum number of stages in which the cured film remains. The transmittance was determined from the number of remaining stages according to Table 3, and the conversion sensitivity was calculated by using the following formula.
Conversion sensitivity (mJ / cm ² ) = Integrated exposure (3000 mJ / cm ² ) x Transmittance (%)
Table 4 shows the number of remaining stages and the conversion sensitivity.

From the results in Table 4 above, the polymerizable composition containing the carbamoyloxime compound of the present invention has a large number of remaining stages (high curability) as compared with the comparative polymerizable composition, and therefore has a high photobase generation efficiency. It can be cured with a low exposure and is highly sensitive to UV-LED light sources. Therefore, it is clear that the compound of the present invention is excellent as a polymerization initiator.

Claims (10)

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

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are Independently, hydrogen atom, halogen atom, cyano group, nitro group, -OR ¹⁶ , -COOR ¹⁶ , -CO-R ¹⁶ , -SR ¹⁶ , hydrocarbon group with 1 to 20 carbon atoms, 2 to 2 carbon atoms. Represents 20 heterocyclic-containing groups or groups represented by the following general formula (II).
R ¹⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms, and when a plurality of R ^16s are present in the molecule, they may be the same. May be different
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15 and ^{R 16} are carbonized Number of carbon atoms in which one or more hydrogen atoms in a hydrogen group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ¹⁷ , -COOR ¹⁷ , -CO-R ¹⁷ or -SR ^17. It may be a group of 1 to 20
R ¹⁷ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group. Represents a group with 1 to 20 atoms, and if there are multiple R ^{17s in} the molecule, they may be the same or different.
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16 and ^{R 17} is one or two or more methylene groups in the hydrocarbon group, -O -, - CO -, - COO -, - OCO -, - NR 18 -, - NR 18 CO- or -S- substituted It may be a group having 1 to 20 carbon atoms.
R ¹⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^18s are present 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, R 11} And R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ are independently connected to each other to form a ring consisting of hydrogen and carbon atoms with 3 to 10 carbon atoms. You may be
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, of ^{R 14} and ^{R 15,} 1 or more Is a group represented by the following general formula (II), and when there are a plurality of groups represented by the general formula (II) in the molecule, they may be the same group or different groups. Good. )

(In the formula, R ²⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms.
X ¹ represents −NR ²¹ R ²² or a 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 or a hydrocarbon group having 1 to 20 carbon atoms.
In R ²⁰ , R ²¹ and R ²² , one or more of the hydrogen atoms in the hydrocarbon group are halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ²³ , -COOR ²³ , -CO-R ^23. Alternatively, it may be a group having 1 to 20 carbon atoms substituted with −SR ²³ .
R ²³ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group. It represents a group with 1 to 20 atoms, and when a plurality of R ^23s are present in the group, they may be the same or different.
In R ²⁰ , R ²¹ , R ²² and R ²³ , one or more of the methylene groups in the hydrocarbon group are -O-, -CO-, -COO-, -OCO-, -NR ^24- , It may be a group having 1 to 20 carbon atoms substituted with −NR ²⁴ CO− or −S−.
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ²⁴ are present in the group, they may be the same or different.
R ²¹ and R ²² are connected to each other and have a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom. It may form 10 rings,
n represents 0 or 1 and represents
* Represents a bond. )

(In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are independently carbonized with a hydrogen atom and 1 to 20 carbon atoms, respectively. Represents a hydrogen group
In R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ , one or more of the hydrogen atoms in the hydrocarbon group are halogen atoms. It may be a group having 1 to 20 carbon atoms substituted with a cyano group, a nitro group, a hydroxyl group, -OR ⁴¹ , -COOR ⁴¹ , -CO-R ⁴¹ or -SR ⁴¹ .
R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^41s are present in the group, they may be the same or different.
In R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ , one or more of the methylene groups in the hydrocarbon group are -O-. , -CO -, - COO -, - OCO -, - NR 42 -, - NR 42 CO- or -S- in may be a substituted group having 1 to 20 carbon atoms,
R ⁴² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^42s are present in the group, they may be the same or different.
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ are independently linked to each other and are derived from hydrogen, nitrogen and carbon atoms, respectively. It may form a ring having 2 to 10 carbon atoms, or a ring having 2 to 10 carbon atoms composed of hydrogen atom, oxygen atom, nitrogen atom and carbon atom.
* Represents a bond. ) Among the general formula R ³ in ^(I), R ⁸ and R ^13, carbamoyl oxime compound according to claim 1 or one is a group represented by the general formula (II). X ¹ in the general formula (II) is −NR ²¹ R ²² .
R ²¹ and R ²² are connected to each other and have a ring having 2 to 10 carbon atoms consisting of hydrogen atom, nitrogen atom and carbon atom or a ring having 2 to 10 carbon atoms, oxygen atom, nitrogen atom and carbon atom having 2 carbon atoms. The carbamoyl oxime compound according to claim 1 or 2, which forms a ring of 10. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R in the general formula (I) The carbamoyloxime compound according to any one of claims 1 to 3, wherein any one or more of ¹⁵ is −CO-R ¹⁶ . A latent base generator containing the carbamoyloxime compound according to any one of claims 1 to 4. A polymerization initiator containing the carbamoyloxime compound according to any one of claims 1 to 4. A polymerizable composition containing the carbamoyloxime compound and the polymerizable compound according to any one of claims 1 to 4. The polymerizable compound is an epoxy resin or an ethylenically unsaturated compound, a mixture containing an epoxy resin and a phenol resin, a mixture containing an epoxy resin and a thiol compound, or a mixture containing an ethylenically unsaturated compound and a thiol compound. The polymerizable composition according to claim 7. A cured product of the polymerizable composition according to claim 7 or 8. A method for producing a cured product, which comprises a step of irradiating the polymerizable composition according to claim 7 or 8 with energy rays.