TW202130616A - 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 capable of simultaneously generating a base and an active species (radical) having a high reactivity. The present invention provides a carbamoyl oxime compound having, in the molecule, a group represented by general formula (I) and an optical radical generating group not having a carbamoyl oxime group. The carbamoyl oxime compound according to the present invention is useful as a polymerization initiator and a latent base generating agent. When the compound according to the present invention is incorporated in a polymerizable composition as a polymerization initiator, higher adhesiveness and post-light irradiation curing properties are obtained as compared to a polymerizable composition containing a conventional optical base generating agent. (Refer to the description for the definitions of the symbols in the formula. * represents an atomic bond.).

Description

Carbamethoxime compound and polymerization initiator and polymerizable composition containing the compound

The present invention relates to a carbamate 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, which 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, etc.

According to the difference of the active species generated by the energy ray (light) irradiation, the photopolymerization initiator is divided into a photoradical generator, a photoacid generator, and a photobase generator. The advantage of the light radical generator is that the curing speed is relatively fast, and no active species will remain after curing. On the other hand, the disadvantage is that oxygen will cause curing inhibition, so an oxygen barrier layer must be provided when the film is cured. The advantage of the photoacid generator is that it will not be inhibited by the hardening caused by oxygen. On the other hand, its disadvantage is that the acid of the active species remains, which causes the corrosion of the metal substrate or the modification of the resin after hardening. Photobase generators are not susceptible to curing inhibition by oxygen and corrosion caused by residual active species, and have attracted attention. However, compared with photoacid generators, they generally have the problem of low sensitivity (low curability). The photobase generator is described in Patent Documents 1 and 2, for example. Among them, Patent Document 1 describes a carbamate compound as a compound having photobase generation ability. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] US2015/064623A1 [Patent Document 2] Japanese Patent Laid-Open No. 2013-163670

[The problem to be solved by the invention]

However, the conventional carbamate oxime compounds have low reactivity of the base species emitted by light irradiation and insufficient initial hardening properties, so they are difficult to use in applications such as adhesives. The subject of the present invention is to provide a compound capable of generating reactive species (radicals) rich in reactivity while generating a base. [Technical means to solve the problem]

After hard research, the present invention provides the following [1] to [10] to achieve the above-mentioned object.

(式中，R¹ 表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基、碳原子數2～20之含雜環基、或者該烴基或該含雜環基中之氫原子之1個或2個以上被取代為選自下述群I之一價基而成的基，或者 表示該烴基、該含雜環基或其等被取代為選自群I之基而成之基中之亞甲基之1個或2個以上經取代為選自下述群II之二價基而成的基， X¹ 表示-NR² R³ 、或者下述通式(a)或下述通式(b)所表示之基， R² 及R³ 分別獨立地表示碳原子數1～20之烴基、或者該烴基中之氫原子之1個或2個以上被取代為選自下述群I之一價基而成的基，或者 表示該烴基或該烴基被取代為選自群I之基而成之基中之亞甲基之1個或2個以上經取代為選自下述群II之二價基而成的基， R² 與R³ 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， 群I係鹵素原子、氰基、硝基、羥基、-OR⁴ 、-COOR⁴ 、-CO-R⁴ 或-SR⁴ ， R⁴ 表示氫原子、碳原子數1～20之烴基、或者該烴基中之1個或2個以上氫原子被鹵素原子、氰基、硝基或羥基取代而成之碳原子數1～20之基，或者 表示該烴基或該烴基被鹵素原子、氰基、硝基或羥基取代而成之基中之亞甲基之1個或2個以上經取代為選自下述群II之二價基而成的基，於基中存在複數個R⁴ 之情形時，其等可相同，亦可不同， 群II係-O-、-CO-、-COO-、-OCO-、-NR⁵ -、-NR⁵ CO-及-S-， R⁵ 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R⁵ 之情形時，其等可相同，亦可不同， n表示0或1， *表示鍵結鍵) [化2]

(式中，R¹¹ 、R¹² 、R¹³ 、R¹⁴ 、R¹⁵ 、R¹⁶ 、R¹⁷ 、R¹⁸ 、R¹⁹ 及R²⁰ 分別獨立地表示氫原子、碳原子數1～20之烴基、或者該烴基中之氫原子之1個或2個以上被取代為選自上述群I之一價基而成的基，或者 表示該烴基或該烴基被取代為選自群I之基而成之基中之亞甲基之1個或2個以上經取代為選自上述群II之二價基而成的基， R¹¹ 與R¹² 、R¹³ 與R¹⁴ 、R¹⁵ 與R¹⁶ 、R¹⁷ 與R¹⁸ 、及R¹⁹ 與R²⁰ 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)[1] A carbamethoxime compound having a group represented by the following general formula (I) and a photoradical generating group that does not have a carbamethoxime group in the same molecule. [化1]

(In the formula, R ¹ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, a heterocyclic group with 2 to 20 carbon atoms, or the hydrocarbon group or the heterocyclic group One or two or more of the hydrogen atoms are substituted with a monovalent group selected from the following group I, or it means that the hydrocarbon group, the heterocyclic group, or the like is substituted with a group selected from the group I One or two or more of the methylene groups in the resulting group are substituted with divalent groups selected from the following group II, X ¹ represents -NR ² R ³ , or the following general formula (a ) Or a group represented by the following general formula (b), R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or one or more of the hydrogen atoms in the hydrocarbon group is substituted A group formed from a monovalent group in the following group I, or means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group is substituted with a group selected from the group I are substituted The group formed from the divalent group of the following group II, R ² and R ³ may be connected to each other to form a carbon atom ring containing a hydrogen atom, a nitrogen atom and a carbon atom, or a hydrogen atom, an oxygen atom , Nitrogen atom and carbon atom ring with 2-10 carbon atoms, Group I is halogen atom, cyano group, nitro group, hydroxyl group, -OR ⁴ , -COOR ⁴ , -CO-R ⁴ or -SR ⁴ , R ⁴ It represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a group with 1 to 20 carbon atoms in which one or more of the hydrogen atoms in the hydrocarbon group is substituted by a halogen atom, a cyano group, a nitro group or a hydroxyl group, Or it means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group substituted by a halogen atom, a cyano group, a nitro group or a hydroxyl group are substituted with a divalent group selected from the following group II When there are multiple R ⁴ in the base, they can be the same or different. Group II is -O-, -CO-, -COO-, -OCO-, -NR ⁵ -, -NR ⁵ CO- and -S-, R ⁵ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R ⁵ in the group, they may be the same or different. n represents 0 or 1, *Indicates a bond key) [化2]

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or One or more of the hydrogen atoms in the hydrocarbyl group is substituted with a monovalent group selected from the above group I, or it means the hydrocarbyl group or the hydrocarbyl group is substituted with a group selected from the group I One or more of the methylene groups are substituted with divalent groups selected from the above group II, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be independently connected to each other to form a ring with 2 to 10 carbon atoms containing hydrogen, nitrogen, and carbon atoms, or a ring containing hydrogen, oxygen, nitrogen, and carbon atoms. A ring with 2 to 10 carbon atoms, * indicates a bonding bond)

(式中，A¹ 表示碳原子數6～20之芳香族環結構， R³¹ 表示上述通式(I)所表示之基， R³² 表示不具有胺甲醯肟基之光自由基產生基、被不具有胺甲醯肟基之光自由基產生基取代而成之碳原子數1～20之烴基、被不具有胺甲醯肟基之光自由基產生基取代而成之碳原子數2～20之含雜環基、或者該烴基或該含雜環基中之氫原子之1個或2個以上被取代為選自下述群III之一價基而成的基，或者 表示該烴基、該含雜環基或其等被取代為選自群III之基而成之基中之亞甲基之1個或2個以上經取代為選自下述群IV之二價基而成的基， R³³ 分別獨立地表示鹵素原子、硝基、氰基、碳原子數1～20之烴基、碳原子數2～20之含雜環基、或者該烴基或該含雜環基中之氫原子之1個或2個以上被取代為選自下述群III之一價基而成的基，或者 表示該烴基、該含雜環基或其等被取代為選自群III之基而成之基中之亞甲基之1個或2個以上經取代為選自下述群IV之二價基而成的基， 群III係鹵素原子、氰基、硝基、羥基、-OR³⁴ 、-COOR³⁴ 、-CO-R³⁴ 或-SR³⁴ ， R³⁴ 表示氫原子、碳原子數1～20之烴基、或者烴基中之1個或2個以上氫原子被鹵素原子、氰基、硝基或羥基取代而成之碳原子數1～20之基，或者 表示該烴基或者該烴基被鹵素原子、氰基、硝基或羥基取代而成之基中之亞甲基之1個或2個以上經取代為選自上述群IV之二價基而成的基，於基中存在複數個R³⁴ 之情形時，其等可相同，亦可不同， 群IV係-O-、-CO-、-COO-、-OCO-、-NR³⁵ -、-NR³⁵ CO-或-S-， R³⁵ 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R³⁵ 之情形時，其等可相同，亦可不同， a表示1～19之整數，於a為2以上之整數之情形時，存在複數個之R³¹ 可相同，亦可不同， b表示1～19之整數，於b為2以上之整數之情形時，存在複數個之R³² 可相同，亦可不同， c表示0～18之整數，於c為2以上之整數之情形時，存在複數個之R³³ 可相同，亦可不同， a＋b＋c為20以下)[2] The aminomethoxime compound as described in [1], which has a structure represented by the following general formula (II). [化3]

(In the formula, A ¹ represents an aromatic ring structure having 6 to 20 carbon atoms, R ³¹ represents a group represented by the above general formula (I), R ³² represents a photo radical generating group without a carbamate group, A hydrocarbon group with 1 to 20 carbon atoms substituted by a photo-radical generating group without a carbamate group, and a carbon number of 2 to substituted by a photo radical generating group without a carbamate group 20 of the heterocyclic group, or one or more of the hydrogen atoms in the hydrocarbon group or the heterocyclic group is substituted with a monovalent group selected from the following group III, or represents the hydrocarbon group, One or two or more of the methylene groups in the heterocyclic group or the group in which the heterocyclic group is substituted with a group selected from group III are substituted with a divalent group selected from the following group IV , R ³³ each independently represents a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, a heterocyclic group with 2 to 20 carbon atoms, or a hydrogen atom in the hydrocarbon group or the heterocyclic group One or two or more of them are substituted with a group selected from the following group III monovalent group, or it means that the hydrocarbon group, the heterocyclic group, or the like is substituted with a group selected from group III One or two or more of the methylene groups in the group are substituted with divalent groups selected from the following group IV. Group III is a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ³⁴ ,- COOR ³⁴ , -CO-R ³⁴ or -SR ³⁴ , R ³⁴ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or one or more of the hydrogen atoms in the hydrocarbon group is replaced by a halogen atom, a cyano group, a nitro group, or A group with 1 to 20 carbon atoms substituted by a hydroxy group, or means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group substituted by a halogen atom, a cyano group, a nitro group, or a hydroxy group Substitution is a group formed by a divalent group selected from the above group IV. When there are plural R ³⁴ in the group, they may be the same or different. Group IV is -O-, -CO-, -COO -, -OCO-, -NR ³⁵ -, -NR ³⁵ CO- or -S-, R ³⁵ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and when there are more than one R ³⁵ in the group, etc. May be the same or different, a represents an integer of 1-19, when a is an integer of 2 or more, there ^{may be a plurality of R 31} which may be the same or different, b represents an integer of 1-19, where b is In the case of an integer of 2 or more, a plurality of R ³² may be the same or different, and c represents an integer from 0 to 18. When c is an integer of 2 or more, there ^{may be a plurality of R 33 that} may be the same, also Can be different, a＋b＋c is less than 20)

[3] The aminomethoxime compound as described in [2], wherein A ¹ is a structure represented by the following general formula (III).

(通式(III)中，Y¹ 表示氧原子、硫原子、硒原子、CR⁴¹ R⁴² 、CO、NR⁴³ 或PR⁴⁴ ， Y² 表示單鍵、無鍵、氧原子、硫原子、硒原子、CR⁴¹ R⁴² 、CO、NR⁴³ 或PR⁴⁴ ， R⁴¹ 、R⁴² 、R⁴³ 及R⁴⁴ 分別獨立地表示氫原子、碳原子數1～20之烴基、碳原子數2～20之含雜環基、該烴基或該含雜環基中之氫原子之1個或2個以上被取代為選自下述群V之一價基而成的基，或者表示該烴基、該含雜環基或其等被選自群V之基取代而成之基中之亞甲基之1個或2個以上經取代為-O-或-CO-而成的基， 群V係鹵素原子、硝基、氰基、羥基、羧基或碳原子數2～20之雜環基)[化3A]

(In the general formula (III), Y ¹ represents oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , Y ² represents single bond, no bond, oxygen atom, sulfur atom, selenium atom , CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, and a heterogeneous group with 2 to 20 carbon atoms One or more of the hydrogen atoms in the cyclic group, the hydrocarbon group, or the heterocyclic group is substituted with a monovalent group selected from the following group V, or it represents the hydrocarbon group or the heterocyclic group Or a group in which one or more of the methylene groups in a group substituted by a group selected from group V are substituted with -O- or -CO-, group V is a halogen atom or a nitro group , Cyano group, hydroxyl group, carboxyl group or heterocyclic group with 2-20 carbon atoms)

[4] The carbamate compound as described in any one of the above [1] to [3], wherein the photo radical generating group having no carbamate group is the following general formula (IVa), ( The group represented by IVb), (IVc), (IVd), (IVe), (IVf) or (IVg).

(通式(IVa)、(IVb)、(IVc)、(IVd)、(IVe)、(IVf)及(IVg)中， R⁵¹ 表示OR⁸¹ 、NR⁸² R⁸³ 或碳原子數2～20之含雜環基， R⁵² 及R⁵³ 分別獨立地表示R⁸¹ 或OR⁸¹ ， R⁵² 與R⁵³ 可鍵結而形成環， R⁸¹ 、R⁸² 及R⁸³ 分別獨立地表示氫原子或碳原子數1～20之烴基，R⁵⁵ 、R⁵⁶ 、R⁵⁸ 、R⁵⁹ 、R⁶¹ 、R⁶² 、R⁶⁴ 、R⁶⁵ 及R⁷¹ 表示碳原子數6～20之芳基， R⁵⁴ 、R⁵⁷ 、R⁶⁰ 、R⁶³ 、R⁶⁶ 及R⁶⁷ 分別獨立地表示碳原子數6～20之伸芳基或單鍵， R⁶⁸ 表示碳原子數1～20之烴基， R⁶⁹ 及R⁷⁰ 分別獨立地表示R⁸¹ 或OR⁸¹ ， *表示鍵結鍵)[化3B]

(In the general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf) and (IVg), R ⁵¹ represents OR ⁸¹ , NR ⁸² R ⁸³ or a carbon number of 2-20 Containing a heterocyclic group, R ⁵² and R ⁵³ each independently represent R ⁸¹ or OR ⁸¹ , R ⁵² and R ⁵³ may bond to form a ring, R ⁸¹ , R ⁸² and R ⁸³ each independently represent a hydrogen atom or the number of carbon atoms A hydrocarbon group of 1-20, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ and R ⁷¹ represent an aryl group with 6 to 20 carbon atoms, R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ and R ⁶⁷ each independently represent an aryl group having 6 to 20 carbon atoms or a single bond, R ⁶⁸ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ⁶⁹ and R ⁷⁰ each independently represent R ⁸¹ or OR ⁸¹ , * means bonding key)

[5] A latent base generator containing the carboxamide compound as described in any one of [1] to [4] above.

[6] A polymerization initiator characterized by containing the carbamate compound as described in any one of [1] to [4] above.

[7] A polymerizable composition containing the carbamate compound and polymerizable compound as described in any one of [1] to [4] above.

[8] The polymerizable composition described above, which is any one of the following (1) to (5). (1) A polymerizable composition containing the polymerization initiator described in [6] and an epoxy resin. (2) A polymerizable composition containing the polymerization initiator described in [6] and an ethylenically unsaturated compound. (3) A polymerizable composition containing the polymerization initiator described in [6], an epoxy resin, and a phenol resin. (4) A polymerizable composition containing the polymerization initiator described in [6], an epoxy resin, and a thiol compound. (5) A polymerizable composition containing the polymerization initiator described in [6], an ethylenically unsaturated compound, and a thiol compound.

[9] A cured product obtained from the polymerizable composition as described in [7] or [8] above.

[10] A method for producing a cured product, which has a step of irradiating the polymerizable composition as described in [7] or [8] with energy rays. [Effects of Invention]

The amine methyl oxime compound of the present invention has the ability to generate free radicals in addition to higher alkali generation efficiency. When it is introduced into the polymerizable composition as a polymerization initiator, it is combined with the previous photobase generator. Compared with the polymerizable composition, the adhesiveness and curability just after light irradiation are higher. Therefore, the polymerizable composition containing the carbamate compound of the present invention can be used as an adhesive.

Hereinafter, preferred embodiments of the present invention will be described in detail. There are no limitations on the preferred configurations described below, and two or more or three or more configurations can be combined. Furthermore, in this specification, unless otherwise specified, the hydrogen atom in the hydrocarbon group having N1 to N2 carbon atoms or the heterocyclic group having N3 to N4 carbon atoms is substituted with a substituent containing carbon atoms It is preferable that the group formed includes the number of carbon atoms of the substituent, and is within the specifications of the number of carbon atoms N1 to N2, N3 to N4 specified at the beginning (N1, N2, N3, N4 are as described in the specification). Numerical value).

The carbamethoxime compound of the present invention is a carbamethoxime compound having a group represented by the above general formula (I) and a photo-radical generating group without a carbamate group in the same molecule. There are geometric isomers produced by the double bond of the oxime in the above-mentioned carbamethoxime compounds, but they are not distinguished. That is, in this specification, the aminoformoxime compound of the present invention, and the following compounds and exemplified compounds which are preferred forms of the compound represent a mixture of isomers or any of them, and are not limited to the structure shown的isomers. Hereinafter, the aminomethoxime compound of the present invention is also referred to simply as "the compound of the present invention". Furthermore, the photo-radical generating group which does not have a carbamate group means a group other than the carbamate group that generates free radicals by irradiating light (active energy) such as ultraviolet rays. The compound of the present invention has at least one photo-radical generating group that does not have a carboxime group in the part of the molecule other than the group represented by the general formula (I). The carboxamide compound of the present invention has a higher photobase generation efficiency due to the high photodecomposition efficiency generated by the specific carboxamide group and the irreversibility of the subsequent alkali species release. Furthermore, in the following, "general formula" is sometimes simply described as "formula".

In the present invention, when there are plural groups represented by the formula (I), when there are plural ^{R 2} to R ⁵ used in the description of ^{R 1} , n, X ^{1 and the like, they are} They may be the same or different. Similarly, when there are a plurality of photo-radical generating groups that do not have a carbamate group, when ^{there are plural R 51} to R ⁸¹ used in the description, they may be the same or may be the same. different.

As each of the above-mentioned halogen atoms described in the description of the above-mentioned formula (I), the above-mentioned formula (II), and the above-mentioned formula (III), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be exemplified.

As the above-mentioned formula (I), the above-mentioned formula (a), the above-mentioned formula (b), the above-mentioned formula (II), the above-mentioned formula (III) and the above-mentioned formula (IVa), (IVb), (IVc), (IVd), ( IVe), (IVf) and (IVg) described in each of the above-mentioned hydrocarbon groups with 1 to 20 carbon atoms, for example: aliphatic hydrocarbon groups with 1 to 20 carbon atoms and aromatics with 6 to 20 carbon atoms From the viewpoint of sensitivity and solubility, the group hydrocarbon group is particularly preferably an aliphatic hydrocarbon group having 1 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, and pentyl. , Isopentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecane Alkyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and other alkyl groups; cyclopentyl, cyclohexyl and other cycloalkyl groups; and cyclohexyl methyl and other cycloalkyl groups An alkyl group and 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, that is, an unsaturated aliphatic hydrocarbon group, etc., from the standpoint of solubility and sensitivity, especially Preferably, it has about 2 to 8 carbon atoms. Particularly preferred is a compound in which R ¹ of the formula (I) is an aliphatic hydrocarbon group having 2 to 8 carbon atoms because of its excellent solubility and sensitivity. The aliphatic hydrocarbon group having 2 to 8 carbon atoms is particularly preferably an alkyl group having 2 to 8 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group. Furthermore, in terms of solubility, a compound in which R ³³ of the formula (II) is an aliphatic hydrocarbon group having 2 to 8 carbon atoms is particularly preferable. In terms of solubility, R ³³ of formula (II), for example, is particularly preferably R ^{43 of NR 43 when A 1} of formula (II) is a carbazole ring. The aliphatic hydrocarbon group having 2 to 8 carbon atoms is particularly preferably an alkyl group having 2 to 8 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group. ^{Also, in terms of sensitivity, R 81} , R ⁸² and R ^{83 in} formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf) and (IVg) are particularly preferred The represented group is a compound of an aliphatic hydrocarbon group having 1 to 8, especially 1 to 3 carbon atoms. ^{In addition, when R 32 in} the compound represented by the formula (II) or the following formula (III-1) is the formula (IVf), in terms of solubility, it is particularly preferably in the formula (IVf) R ⁶⁸ is a compound of an aliphatic hydrocarbon group having 2 to 8 carbon atoms.

基、苄基、萘基、菲基、芘基及聯苯基等。As the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group,

Benzyl, benzyl, naphthyl, phenanthryl, pyrenyl, biphenyl, etc.

As the description of the above formula (I), the above formula (II), the above formula (III) and the above formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf) and (IVg) Each of the above-mentioned heterocyclic groups having 2 to 20 carbon atoms described in, for example, tetrahydrofuranyl, dioxolane, tetrahydropiperanyl, morpholinyl, thiazolyl, furyl, and thienyl , Methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolinyl, pyrazolidinyl, piperidinyl and piperidinyl And other heterocyclic groups and groups containing such heterocyclic groups. Specifically, the heterocyclic group-containing group refers to a heterocyclic group or a group formed by bonding a heterocyclic group and a hydrocarbon group. The heterocyclic group refers to a group formed by removing a hydrogen atom from the heterocyclic ring of a heterocyclic compound when it is monovalent. Condensed rings of heterocycles and aromatic rings (indole, etc.) are also included in heterocycles. In the case where the heterocyclic group is a group formed by bonding a heterocyclic group and a hydrocarbon group, the heterocyclic group may be formed by substituting one or more of the hydrogen atoms in the heterocyclic group by the above-mentioned aliphatic hydrocarbon group The group may also be a group in which one or two or more hydrogen atoms in the aliphatic hydrocarbon group are substituted with the heterocyclic group. When the heterocyclic group has a structure other than the heterocyclic ring, the number of carbon atoms of the heterocyclic group includes not only the number of carbon atoms of the heterocyclic ring, but also the number of carbon atoms derived from structures other than the heterocyclic ring.

R ¹ , R ² , R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18 and One or two or more hydrogen atoms in the hydrocarbon group with 1 to 20 carbon atoms represented by R ¹⁹ and R ²⁰ (hereinafter also ^{referred to as "R 1 etc.") are substituted with monovalents selected from the above group I} Examples of the groups formed by the above-mentioned hydrocarbon groups with 1 to 20 carbon atoms include halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ⁴ , -COOR ⁴ ,- CO-R ⁴ or -SR ⁴ substituted group. When ^{the hydrocarbon group represented by R 1} and the like has a substituent selected from group I, the number of carbon atoms of ^{the entire group represented by R 1} and the like including the carbon number of the substituent is preferably 1-25, Especially preferably, it is 1-20. In addition, R ⁴ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and the carbon atom number is 1 to The group of 20, or means that one or more of the methylene groups in the hydrocarbon group or the hydrocarbon group substituted by a halogen atom, a cyano group, a nitro group, or a hydroxyl group are substituted with a divalent group selected from the above group II Examples of the group formed by the group include groups having 1 to 20 carbon atoms as a whole. The ^{number of carbon atoms of R 4} is preferably 1-10, more preferably 1-5, and particularly preferably 1-3.

As one or more hydrogen atoms of the heterocyclic group having 2 to 20 carbon atoms represented ^{by R 1} in the above formula (I), etc. are substituted with a monovalent group selected from the above group I Examples of the group include one or two or more hydrogen atoms of the above-mentioned heterocyclic group with 2 to 20 carbon atoms with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁴ , -COOR ⁴ ,- CO-R ⁴ or -SR ⁴ substituted group. When the ^{heterocyclic group represented by R 1} and the like has a substituent selected from group I, the number of carbon atoms of ^{the entire group represented by R 1} and the like including the number of carbon atoms of the substituent is preferably 2-25, particularly preferably 2-20.

^{As a hydrocarbon group with 1 to 20 carbon atoms represented by R 1 of the} above formula (I), etc., or one or more methylene groups in the group formed by being substituted with groups selected from group I Substitution is a group formed by a divalent group selected from the above group II, for example: the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a group formed by substituting a hydrogen atom in the hydrocarbon group by a group selected from the group I One or more methylene groups are substituted with -O-, ^{-CO-, -COO-, -OCO-, -NR 5} -, -NR ⁵ CO- or -S-. When ^{the methylene group in the hydrocarbon group represented by R 1} etc. or a group substituted with a group selected from group I is substituted with a divalent group selected from the above group II, R ¹ etc. represent The number of carbon atoms of the entire group is preferably 1-25, particularly preferably 1-20, and still more preferably 1-18. In addition, R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R ⁵ in the group, they may be the same or different. The ^{number of carbon atoms of R 5} is preferably 1-10, more preferably 1-5, and particularly preferably 1-3.

^{As one} or more of the heterocyclic group containing 2 to 20 carbon atoms represented by R 1 etc. in the above formula (I) or substituted with a group selected from the group I The methylene group is substituted with a divalent group selected from the above group II, for example: the above-mentioned heterocyclic group having 2 to 20 carbon atoms or the hydrogen atom in the heterocyclic group is selected from the group One or more of the methylene groups in the group substituted by the group of I have been -O-, ^{-CO-, -COO-, -OCO-, -NR 5} -, -NR ⁵ CO- or -S -Substituted radicals. When ^{the methylene group in the heterocyclic group represented by R 1} etc. or a group substituted with a group selected from group I is substituted with a divalent group selected from the above group II, R ¹ etc. The number of carbon atoms of the entire group represented is preferably 2-25, particularly preferably 2-20, and still more preferably 2-18. In addition, R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R ⁵ in the group, they may be the same or different.

Furthermore, in the present specification, when plural methylene groups in the hydrocarbon group or heterocyclic group are substituted with a group selected from group II or group IV, it is preferably selected from group II or group IV. Substitution in a way that the groups are not adjacent to each other.

R ² and R ³ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R 2 and R 3, R 11 and R 12, R 13 and R 14, R 15 and R 16, and Each of R ¹⁸ , R ¹⁹ and R ²⁰ can be connected to each other to form each of the above-mentioned "rings with 2 to 10 carbon atoms containing hydrogen atoms, nitrogen atoms and carbon atoms" is a skeleton of the ring formed by nitrogen atoms and carbon atoms ring. Examples of the ring containing a hydrogen atom, a nitrogen atom, and a carbon atom with 2 to 10 carbon atoms include a pyrrole ring, a pyrrolidine ring, an imidazole ring, an imidazole pyridine ring, an imidazoline ring, a pyrazole ring, and a pyrazole ring. A pyridine ring, a piperidine ring, a piperidine ring, etc., as each of -NR ² R ³ , -NR ¹¹ R ¹² , -NR ¹³ R ¹⁴ , -NR ¹⁵ R ¹⁶ , -NR ¹⁷ R ¹⁸ , and -NR ¹⁹ R ²⁰ The ring of the nitrogen atom in the person. These rings may have a substituent. As the substituent in this case, the above-mentioned substituents that the heterocyclic group having 2 to 20 carbon atoms may have may be mentioned. The number of carbon atoms 2-10 in "the above-mentioned ring with 2-10 carbon atoms containing hydrogen atoms, nitrogen atoms, and carbon atoms" means the number of carbon atoms constituting the ring. When the ring has a substituent, the number of carbon atoms of the ring including the number of carbon atoms of the substituent is preferably 12 or less, more preferably 10 or less.

R ² and R ³ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R 2 and R 3, R 11 and R 12, R 13 and R 14, R 15 and R 16, and Each of R ¹⁸ , R ¹⁹ and R ²⁰ can be connected to each other to form each of the above-mentioned "rings with 2 to 10 carbon atoms including hydrogen, oxygen, nitrogen, and carbon atoms" based on oxygen atoms, nitrogen atoms, and carbon atoms. The atoms form the backbone of the ring. Examples of the ring containing hydrogen, oxygen, nitrogen, and carbon atoms with 2 to 10 carbon atoms include: morpholine ring, oxazole ring, oxazoline ring, and oxadiazole ring. ^{-NR 2} R ³ in formula (I), NR ¹¹ R ¹² and -NR ¹³ R ¹⁴ in formula (a), and -NR ¹⁵ R ¹⁶ , -NR ¹⁷ R ¹⁸ and -NR in formula (b) The ring of the nitrogen atom in each of ¹⁹ R ^20. These rings may have a substituent. As the substituent in this case, the above-mentioned substituents that the heterocyclic group having 2 to 20 carbon atoms may have may be mentioned. The number of carbon atoms 2 to 10 in "a ring with 2 to 10 carbon atoms containing hydrogen atom, oxygen atom, nitrogen atom, and carbon atom" means the number of carbon atoms constituting the ring. When the ring has a substituent, the number of carbon atoms of the ring including the number of carbon atoms of the substituent is preferably 12 or less, more preferably 10 or less.

In ^{the hydrocarbon group represented by R 4} or R ³⁴ , one or more hydrogen atoms in which one or more hydrogen atoms are substituted by halogen atoms, cyano groups, nitro groups, or hydroxy groups, means groups with 1 to 20 carbon atoms as mentioned above One or more hydrogen atoms of 1-20 hydrocarbon groups are substituted by halogen atoms, cyano groups, nitro groups or hydroxyl groups.

^{The aromatic ring structure with 6 to 20 carbon atoms represented by A 1} in the formula (II) means a structure with 6 to 20 carbon atoms containing an aromatic ring, which contains an aromatic hydrocarbon ring or an aromatic heterocyclic ring base.

The aromatic ring structure containing an aromatic hydrocarbon ring means a structure that does not contain an aromatic heterocycle but contains an aromatic hydrocarbon ring, for example: cyclobutadiene ring, benzene ring, cyclooctatetraene ring, and ring Carbon heptaene ring, cyclooctadecenone ring, naphthalene ring, anthracene ring, triphenylamine structure, diphenyl sulfide structure and sulphur ring, etc.

An aromatic ring structure containing an aromatic heterocyclic ring means a structure containing an aromatic heterocyclic ring, for example: furan ring, thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyridine ring, pyrimidine ring , Pyridine ring, carbazole ring, and indole ring.

In formula (II), when a represents an integer of 1-19, and a is an integer of 2 or more, there ^{may be a plurality of R 31} which may be the same or different, and b represents an integer of 1-19, and b is 2. In the case of the above integers, a plurality of R ³² may be the same or different. When c represents an integer from 0 to 18, and c is an integer of 2 or more, there ^{may be a plurality of R 33s} that are the same or different. Different, but a+b+c is 20 or less. Among them, a+b+c takes the number of bonds in the aromatic ring structure as the upper limit. Among the carbamate oxime compounds of the present invention, the compound of formula (II) whose a is 1 to 3 has excellent sensitivity when used as a latent base generator or polymerization initiator, so it is preferred, and more preferred A is 1 compound. The compound of formula (II) where b is 1 to 3 has excellent sensitivity when used as a latent base generator or polymerization initiator, so it is preferable, and the compound where b is 1 is more preferable. Particularly preferred are compounds in which both a and b are 1. Among the carbamate oxime compounds of the present invention, R ³² in the formula (II) is the above-mentioned compound which does not have an oxime ester group and has a photo radical generating group, which is preferable because of its excellent sensitivity.

When the compound of formula (II) with c being 0 to 3 is used as a latent base generator or polymerization initiator, it has excellent transparency and sensitivity, so it is preferred, and the compound with c being 0 or 1 is particularly preferred. .

The ^{hydrocarbon group with 1 to 20 carbon atoms represented by R 32} substituted by a photo-radical generating group that does not have a carbamoyl oxime group means one or more of the hydrocarbon groups with 1 to 20 carbon atoms The hydrogen atom of which is substituted by a photo-radical generating group that does not have an carboxime group. Where R ³² is a hydrocarbon group with 1 to 20 carbon atoms substituted by the above-mentioned photo-radical generating group, or the methylene group in the hydrocarbon group is substituted with a group selected from group IV, and/or the hydrogen atom in the group is selected In the case of a group substituted from a group of group III, the number of carbon atoms of the ^{entire R 32} including the number of carbon atoms of the substituents is preferably 1-25, particularly preferably 1-20, and most preferably 1～18.

The above-mentioned R ³² represented by the heterocyclic group having 2 to 20 carbon atoms substituted by a photo-radical generating group having no carbamoyl oxime group means one of the heterocyclic group having 2 to 20 carbon atoms A group in which one or more hydrogen atoms are substituted with a photo-radical generating group that does not have a carboxime group. Where R ³² is a heterocyclic group having 2 to 20 carbon atoms substituted by the above-mentioned photo-radical generating group, or the methylene group in the heterocyclic group is substituted with a group selected from group IV, and/or a group In the case where the hydrogen atom is substituted by a group selected from group III, the number of carbon atoms of the ^{entire R 32} including the carbon number of the substituents is preferably 2-25, more preferably 2 ~20.

^{As a hydrocarbon group with 1-20 carbon atoms represented by R 32} in the above formula (II) substituted by a photo-radical generating group not having an aminocarboxime group or 1 to carbon atoms represented by ^{R 33} One or more hydrogen atoms of the 20 hydrocarbon groups are substituted with monovalent groups selected from the above group III, and one or more hydrogen atoms of these hydrocarbon groups can be exemplified by halogens. Atom, cyano group, nitro group, hydroxyl group, -OR ³⁴ , -COOR ³⁴ , -CO-R ³⁴ or -SR ³⁴ substituted. When R ³³ has a substituent selected from the group III that replaces the hydrogen atom in the hydrocarbon group, the ^{number of carbon atoms of the entire R 33} including the substituent is preferably 1-25, more preferably 1-20. In addition, R ³⁴ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or one or more hydrogen atoms in the hydrocarbon group substituted with a halogen atom, a cyano group, a nitro group, or a hydroxy group with 1 A group of -20, or it means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group substituted by a halogen atom, a cyano group, a nitro group, or a hydroxyl group are substituted to be selected from the above group IV The group formed by the valence group may be a group having 1 to 20 carbon atoms as a whole. The ^{number of carbon atoms of R 34} is preferably 1-10, more preferably 1-5, and particularly preferably 1-3.

As the above formula (II) represented by R ³² is substituted by a photo-radical generating group not having a carboxime group, a heterocyclic group containing 2 to 20 carbon atoms or a carbon atom represented by ^{R 33} One or two or more hydrogen atoms of the heterocyclic group containing 2 to 20 are substituted with a monovalent group selected from the above group III. Examples of the heterocyclic group containing 2 to 20 carbon atoms One or more hydrogen atoms in the cyclic group are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR ³⁴ , -COOR ³⁴ , -CO-R ³⁴ or -SR ³⁴ . In the case where R ³³ has a substituent selected from the group III in which a hydrogen atom in the heterocyclic group is substituted, the number of carbon atoms of the entire ^{R 33 including the substituent is preferably 1-25, more preferably 1} ~20. In addition, R ³⁴ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or one or more hydrogen atoms in the hydrocarbon group substituted with a halogen atom, a cyano group, a nitro group, or a hydroxy group with 1 A group of -20, or it means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group substituted by a halogen atom, a cyano group, a nitro group, or a hydroxyl group are substituted to be selected from the above group IV The group formed by the valence group may be a group having 1 to 20 carbon atoms as a whole.

As one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms represented ^{by R 32} or R ³³ in the above formula (II) or the hydrocarbon group being substituted into group III Substitution is a group selected from a divalent group selected from the above group IV, including one or more of the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a group in which the hydrogen atom of the hydrocarbon group is substituted by group III The methylene group is substituted by -O-, ^{-CO-, -COO-, -OCO-, -NR 35} -, -NR ³⁵ CO- or -S-. When R ³³ is a group in which the methylene group of the group III substituted or unsubstituted hydrocarbon group is substituted with a group selected from group IV, the ^{number of carbon atoms of R 33} as a whole is preferably 1-25 , More preferably 1-20, particularly preferably 1-18. In addition, R ³⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of R ³⁵ in the group, they may be the same or different. The ^{number of carbon atoms of R 35} is preferably 1-10, more preferably 1-5, and particularly preferably 1-3.

Examples of the above formula (II) wherein one or two or more of the methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted with divalent groups selected from the above group IV, for example For example, one or two or more methylene groups in the above-mentioned heterocyclic group containing 2 to 20 carbon atoms are -O-, -CO-, -COO-, -OCO-, -NR ³⁵ -, -NR ³⁵ CO- or -S- substituted group. When R ³³ is a group in which the methylene group in the heterocyclic group-containing group substituted or unsubstituted by group III is substituted by a group selected from group IV, the number of carbon atoms of ^{R 33 as a whole is preferably} 2-25, more preferably 2-20, particularly preferably 2-18. In addition, R ³⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of R ³⁵ in the group, they may be the same or different.

When A ¹ of the above formula (II) is the structure represented by the above formula (III), when used as a latent base generator or polymerization initiator, the sensitivity is higher, and the efficiency of base and free radical generation is higher. , So it is particularly good. Particularly preferred is a compound represented by the following formula (III-1).

(式中，R⁹⁰ 、R⁹¹ 、R⁹² 及R⁹³ 中任一者表示上述通式(I)所表示之基，其餘表示氫原子或與式(III)之R³³ 含義相同之基。 R⁹⁴ 、R⁹⁵ 、R⁹⁶ 及R⁹⁷ 中任一者表示與式(III)之R³² 相同含義之基，其餘表示氫原子或與式(III)之R³³ 含義相同之基；Y¹ 及Y² 與式(III)含義相同)[化3C]

(In the formula, ^{any one of R 90} , R ⁹¹ , R ⁹² and R ⁹³ represents a group represented by the above general formula (I), and the rest represent a hydrogen atom or a group having the same meaning as ^{R 33 in the formula (III). R Any one of 94} , R ⁹⁵ , R ⁹⁶ and R ^{97 represents a group having the same meaning as R 32 of} formula (III), and the rest represents a hydrogen atom or a group having the same meaning as ^{R 33 of formula (III); Y 1} and Y ² has the same meaning as formula (III))

As a preferable structure represented by formula (III) and formula (III-1), in order to make the sensitivity good, for example: diphenyl sulfide structure (Y ¹ is a sulfur atom, Y ² is a bondless), a ring (Y ¹ is CR ⁴¹ R ⁴² , Y ² is a single bond) and a carbazole ring (Y ¹ is NR ⁴³ , Y ² is a single bond), and particularly preferably a fluorine ring or a carbazole ring.

Compounds in formulas (III) and (III-1) in which Y ² is a single bond are preferred because they have excellent sensitivity when used as a latent base generator or polymerization initiator.

^{When Y 2} in the formula (III) has no bond, it means the group represented by the following formula (III').

(Y¹ 與式(III)中之Y¹ 相同)[化4]

(Y ¹ in the formula (III) Y same ¹⁾

When the compound represented by the formula (III) with a carbazole ring is used as a latent base generator or polymerization initiator, the sensitivity is also high in long-wavelength light sources above 365 nm, even if it is used in combination with pigments, etc. , The sensitivity is also higher, so it is better.

When the compound represented by the formula (III) is a diphenyl sulfide structure, when used as a latent base generator or polymerization initiator, the sensitivity is high and the transparency is excellent, so it is preferable.

When the compound represented by the formula (III) with a sulphur ring is used as a latent base generator or polymerization initiator, it has higher sensitivity and excellent transparency, so it is preferable.

The photo-radical generating group that does not have a carbamoyl oxime group in the compound of the present invention is not particularly limited. In order to have a higher ability to generate free radicals against ultraviolet rays, it is preferably in the above formulas (IVa) to (IVg) The base represented by any one. In the base represented by any one of the above formulas (IVa) to (IVg), if the sensitivity is to be higher, (IVa) and (IVf) are preferred, and if the sensitivity to long-wavelength ultraviolet rays is to be higher, Preferred are (IVb), (IVc), (IVd) and (IVe).

In order to make the sensitivity excellent, it is preferable that the photo-radical generating group without carbamate group is a compound of formula (IVa), and it is more preferable that R ⁵¹ in formula (IVa) is OR ⁸¹ , NR ⁸² R ⁸³ or The heterocyclic group-containing compound having 2 to 20 carbon atoms is particularly preferred in which R ⁵¹ in formula (IVa) is NR ⁸² R ⁸³ or the heterocyclic group-containing compound having 2 to 20 carbon atoms.

^{As the heterocyclic group containing 2 to 20 carbon atoms represented by R 51} in the formula (IVa), preferable examples include a heterocyclic group obtained by removing one hydrogen atom from a heterocyclic ring containing a nitrogen atom in the ring skeleton , Or the group formed by bonding the heterocyclic group and the hydrocarbon group. Examples of the heterocyclic ring containing a nitrogen atom in the ring skeleton include: aziridine ring, azetidine ring, azolidine ring, azole ring, azetidine ring, azepane ring, morpholine ring In order to achieve excellent free radical generation efficiency, morpholine ring and thiol ring are particularly preferred, and morpholine ring is particularly preferred. ^{The heterocyclic group having 2 to 20 carbon atoms represented by R 51} in the formula (IVa) is preferably a heterocyclic group obtained by removing one hydrogen atom from a heterocyclic ring containing a nitrogen atom in the ring skeleton, and is particularly preferably a ring A heterocyclic group formed by bonding the nitrogen atom in the skeleton to the carbon atom bonded to R ⁵² and R ^{53 in formula (IVa).} The number of carbon atoms of the heterocyclic group containing 2-20 carbon atoms represented by ^{R 51 is preferably 2-10.}

^{The ring formed by R 52} and R ⁵³ in the above formula (IVa) is not particularly limited, for example, saturated aliphatic such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc. For the ring, the above-mentioned aromatic hydrocarbon ring, the above-mentioned aromatic heterocyclic ring, etc., if it is desired to have higher transparency and higher solubility in solvents, a saturated aliphatic ring is preferred, and the stability of the compound is higher, especially Preferably, it is a cyclohexane ring.

As the aryl group with 6 to 20 carbon atoms represented by ^{R 55} , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ and R ^{71 in} the above formulas (IVa) to (IVg) Examples include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, phenyl, biphenyl, naphthalene substituted by one or more of the above alkyl groups基, anthracene group, etc. The number of carbon atoms of the aryl group is preferably 6-10.

^{As R 54} , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ and R ^{67 in} the above formulas (IVa) to (IVg), the aryl group having 6 to 20 carbon atoms used may be exemplified by the above carbon atoms A group formed by removing one hydrogen atom from an aryl group of 6 to 20, etc. The number of carbon atoms of the arylene group is preferably 6-10.

In terms of solvent solubility and the like, the number of carbon atoms of the hydrocarbon groups represented by ^{R 81} , R ⁸² and R ⁸³ in the above formulas (IVa) to (IVg) is preferably 1-8, particularly preferably 1-3.

As a preferable photo-radical generating group, for example: the following formulas (IVa1)～(IVa5), (IVb1), (IVc1), (IVd1), (IVe1), (IVf1), (IVg1) and (IVh1) ). Among them, in order to combine the photo-radical generating group with the group represented by formula (I), the sensitivity is higher, preferably the photo-radical generating group represented by any one of (IVa1) to (IVa5) and (IVf1) base. In the case of using a light source containing ultraviolet light in the long-wavelength region of 365 nm or more, in order to make the above-mentioned sensitivity higher, (IVb1), (IVc1), (IVd1), (IVe1), (IVf1) and (IVh1) The photo radical generating group represented by any one of them.

[化4A]

The carbamethoxime compound in which the group represented by the above formula (I) is bonded to the benzene ring in the aromatic ring with 6 to 20 carbon atoms represented by ^{A 1 is used as a polymerization initiator.} The exposure amount is hardened, so it is better. Furthermore, in terms of the stability and ease of manufacture of the compound, it is preferable ^{that the aromatic ring with 6 to 20 carbon atoms represented by A 1} has a plurality of benzene rings, and the group represented by formula (I) and A compound in which a light radical generating group is separately bonded to another benzene ring. Particularly preferred is a compound represented by formula (III-1). Among them, from the viewpoint of ease of production, it is preferred that either of R ⁹¹ and R ⁹² represents a group represented by formula (I), and R ⁹⁵ And ^{any one of R 96} is a compound having the same meaning as ^{R 32 in} formula (III).

In addition, the compound of formula (I) where X ¹ is -NR ² R ³ is preferred because of the higher stability of the compound. In order to make the reactivity of generating base higher, it is more preferred that R ² and R ³ interact with each other. Linked to form a carbon atom ring containing a hydrogen atom, a nitrogen atom, and a carbon atom, or a carbon atom ring containing a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom. It is particularly ^{preferable that R 2} and R ³ are linked 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.

In addition, compounds in the formula (I) in which X ¹ is -NR ² R ³ and R ² and R ³ are aliphatic hydrocarbon groups with 2 to 8 carbon atoms are preferred because of their higher solubility.

^{In addition, compounds in which R 32 in} formula (III) and formula (III-1) is a photo-radical generating group without a carbamoyl oxime group are preferred because of their higher sensitivity.

The compound in the above formula (I) where n is 0 is preferred because of its higher stability to heat. The compound in which n in the above formula (I) is 1 is preferable because it hardens with a low exposure amount.

As a specific example of the aminomethoxime compound of this invention, the compound shown by the following No.1-No.181 can be mentioned. However, the present invention is not limited by the following compounds.

.[化5]

.

[化6]

[化7]

[化8]

[化9]

[化10]

[化11]

[化12]

[化13]

[化14]

[化15]

[化16]

[化17]

.[化18]

.

[化19]

[化20]

[化21]

[化22]

[化23]

[化24]

The method for producing the compound of the present invention is not particularly limited. For example, an oxime compound can be obtained by reacting a known ketone compound with 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 with it, thereby obtaining the aminomethoxime compound of the present invention.

It is also possible to produce ^{a compound in which X 1} is -NR ² R ³ , the group represented by the above formula (a) or the above formula (b) by changing the amine used. It is also possible to obtain a compound in which the group represented by formula (I) is introduced at an arbitrary position by using a ketone compound in which a ketone group is introduced at an arbitrary position as a raw material. 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 irradiation or heating of light such as ultraviolet rays, so it can be used as a latent base generator and polymerization initiator, especially as a latent base generator Agent.

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 its use can be exemplified by: pH adjuster, utilization of alkali The catalyst and so on.

In addition, among the above-mentioned polymerization initiators, if the efficiency of generating alkali and free radicals by light irradiation is high, the carbamate compound of the present invention can be used as a photobase generator and a photoradical polymerization initiator. , In order to make the alkali production efficiency very high, it can be especially used as a photobase generator.

The polymerization initiator of the present invention contains at least one compound of the present invention. The polymerization initiator that can be used in combination with the carbamate compound represented by the above formula (I) is not particularly limited, and the previously known photobase generators and photo-radical polymerization initiators can be exemplified.

In order to increase the efficiency of base and free radical generation, the content of the compound represented by the formula (I) in the polymerization initiator is preferably 1-100% by mass, more preferably 50-100% by mass, and more Preferably, it is 70 to 100% by mass.

The polymerizable composition of the present invention includes a polymerization initiator (A) containing at least one compound of the present invention, and a polymerizable compound (B). The content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound (B). 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.

The polymerizable compound (B) used in the present invention may, for example, be 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 base addition reaction, and a radical The polymerizable compound is preferably a photosensitive resin polymerized and hardened by irradiation with energy rays such as ultraviolet rays, or a hardening resin whose hardening temperature is lowered. The above-mentioned anionic polymerizable functional group means a functional group that can generate a base from a photobase generator using active energy rays such as ultraviolet rays and polymerize with the base, and examples thereof include epoxy groups, episulfide groups, and cyclic monomers ( σ-valerolactone, ε-caprolactone), malonate, etc. The reaction in which the base acts as a catalyst or the base addition reaction can be exemplified: the reaction of forming a urethane bond using isocyanate and alcohol, the addition reaction of a compound containing epoxy resin and hydroxyl group, and the reaction containing epoxy resin and carboxyl The addition reaction of acid-based compounds, the addition reaction of epoxy resins and thiol compounds, the Michael addition reaction of (meth)acrylic acid groups, the dehydration condensation reaction of polyamide acid, and the hydrolysis of alkoxysilanes- Polycondensation reaction and so on.

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 an alkali acts as a catalyst or an alkali addition reaction include: polyamide resin (polyimination reaction by dehydration cyclization), epoxy-hydroxyl group (Ring-opening addition reaction), epoxy-carboxylic acid system (ring-opening addition reaction), epoxy-thiol system (ring-opening addition reaction), epoxy-anhydride system (ring-opening polycondensation), Cyanate ester (tricyclic cyclization reaction), cyanate ester-epoxy system (cyclization reaction), cyanate ester-maleimide system (crosslinked copolymerization), oxetane-hydroxyl system (Ring-opening addition reaction), oxetane-carboxylic acid system (ring-opening addition reaction), oxetane-thiol 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-thiol system (ring-opening addition reaction), Episulfide-anhydride series (ring-opening polycondensation), acrylic-thiol series (Miccan addition reaction), methacryl-thiol series (Miccan addition reaction), acrylic-amine series (Miccan addition reaction) Addition reaction), methacryl-amine series (Macco addition reaction), carboxylic acid-hydroxyl series (polyesterification reaction), carboxylic acid-amine series (polyamide reaction), isocyanate-hydroxyl series ( Polyurethane reaction), isocyanate-thiol system (polythiourethane reaction), alkoxysilane system (hydrolysis-polycondensation), etc. As the compound polymerized by radicals, an ethylenically unsaturated compound may be mentioned. In order to make the reactivity higher, 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 order to make the reaction proceed quickly or have good adhesion, a combination of an epoxy resin and a phenol resin can be exemplified, and a combination of an epoxy resin and a thiol compound can be exemplified in order to achieve excellent low-temperature curability. In order to increase the reactivity, a combination of an ethylenically unsaturated compound and a thiol compound can be exemplified.

The epoxy resin is not particularly limited as long as it is a compound having an epoxy group. For example, it may include mononuclear polyphenol compounds such as hydroquinone, resorcinol, catechol, and phloroglucinol. The polyglycidyl ether compound; dihydroxy naphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene 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, oxobisphenol, phenol novolac, o-cresol novolak, ethyl phenol novolak, butyl phenol novolak, octylphenol novolak, resorcinol novolak, Polyglycidyl ether compounds of polynuclear polyphenol compounds such as terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyglycol, thiodiethanol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, Polyhydric alcohol polyglycidyl ether such as bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, Azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid Glycidyl esters of aliphatic, aromatic or cycloaliphatic polybasic acids such as dicarboxylic acid, hexahydrophthalic acid, and endo-methylenetetrahydrophthalic acid, and homopolymers of glycidyl methacrylate or Copolymer; N,N-diglycidyl aniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl o-toluidine, etc. have glycidyl amino groups The epoxy compound; vinyl cyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl ester, 3,4 -Epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate and other rings Epoxides of olefin compounds; epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, epoxidized styrene-butadiene copolymer and other epoxidized conjugated diene polymers, isocyanuric acid three Heterocyclic compounds such as glycidyl esters. In addition, the epoxy resins may be formed by internal crosslinking of prepolymers with terminal isocyanate groups, or may be made of multiple active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphate esters, etc.) High molecular weight. Among the above epoxy resins, in order to have excellent curability, 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 is a compound which has a phenolic hydroxyl group and is not classified as the said epoxy resin. As the phenol resin, in order to have excellent curability, it is preferably a phenol resin having two or more hydroxyl groups in one molecule, and generally known ones can be used. The phenol resin may, for example, be bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak 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, many Functional 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-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 said thiol compound is a compound which has a thiol group and is not classified into the said epoxy resin and the said phenol resin. As the above-mentioned thiol compound, in order to have excellent curability, it is preferably one having two or more thiol groups in one molecule. Preferred specific examples of the thiol compound include: bis(2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis(mercaptomethyl) Benzene, 1,4-bis(mercaptomethyl)benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1, 11-Dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, 1,1,3,3-Tetra(mercaptomethylthio)propane, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, and trimethylolpropane trimercapto Propionate, more preferably exemplified: 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 tetramercaptoacetate. Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1 ,4-Dithiane, 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.

The polyamide resin is a compound having an amide group, and is not classified into the epoxy resin, the phenol resin, and the thiol compound. Examples of the polyamide resin include: ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-ring Hexanetetracarboxylic 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 for resins; as diamines (ortho, meta or p) phenylene diamine, (3,3'- or 4,4'-) diamino diphenyl ether, diamine Benzophenone, (3,3'- or 4,4'-)diaminodiphenylmethane, etc. as raw materials.

The polyurethane resin is a compound having a urethane group and is not classified into the epoxy resin, the phenol resin, the thiol compound, the polyamide resin, and the following ethylenically unsaturated Compound of compound. Examples of the polyurethane resin include polyfunctional isocyanates such as toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and polyether polyols and polyesters. Polyols, polycarbonate polyols, and other polyols (polyfunctional alcohols) as raw materials for resins, etc. Moreover, as said nylon resin, the resin etc. which use cyclic monomers, such as ε-caprolactam and lauryl lactam, as a raw material, etc. are mentioned. Moreover, as 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 ethylenically unsaturated compound is a compound having an ethylenically unsaturated group, and is not classified into the epoxy resin, the phenol resin, the thiol compound, and the polyamide resin. Examples of the ethylenically unsaturated compound 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, methyl maleic acid, fumaric acid, bicycloheptene dicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl Acetic acid, cinnamic acid, sorbic acid, methyl fumaric acid, succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxy Mono(meth)acrylates of polymers with carboxyl and hydroxyl groups at both ends, such as hydroxyethyl]ester and ω-carboxy polycaprolactone mono(meth)acrylate; Alkenate, hydroxypropyl (meth)acrylate-maleate, dicyclopentadiene-maleate, or having 1 carboxyl group and 2 or more (meth)acrylic acid groups Polyfunctional (meth)acrylate and other unsaturated polybasic acids; (meth)-2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, methyl (meth)acrylate, (methyl) )Butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, (meth)acrylic acid Poly(ethoxy)ethyl, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (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 dimethanol di(meth)acrylate, isocyanurate tri((methyl) ) Ethyl acrylate, polyester (meth)acrylate oligomer and other unsaturated monobasic acid and polyol or polyphenol ester; zinc (meth)acrylate, magnesium (meth)acrylate and other unsaturated Metal salts of polybasic acids; maleic anhydride, itaconic anhydride, methyl maleic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride Formic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3- Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl bicycloheptene Anhydrides of unsaturated polybasic acids such as formic anhydride; (meth)acrylamide, methylenebis(meth)acrylamide, diethylenetriamine tri(meth)acrylamide, xylylenediamine (Meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth)acrylamide and other unsaturated monobasic acids and polyamine amides; acrolein and other unsaturated aldehydes; (formaldehyde) Base) acrylonitrile, α-chloroacrylonitrile, dicyandiene, allyl cyanide and other unsaturated nitriles; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, Unsaturated aromatic compounds such as vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; allyl Vinyl alcohol such as 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, Unsaturated imines such as N-phenyl maleimide and N-cyclohexyl maleimide; indene such as indene and 1-methylindene; 1,3-butadiene, Aliphatic conjugated dienes such as isoprene and chloroprene; molecular chains of polymers such as polystyrene, polymethyl (meth)acrylate, poly n-butyl (meth)acrylate, and polysiloxane Macromonomers with mono(meth)acrylic acid groups at the end; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, isocyanide Triallyl urate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and vinyl of polyisocyanate compounds Vinyl epoxy compounds of urethane compounds, vinyl monomers containing hydroxyl groups, 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 Nippon Kayaku Manufacturing); ARONIX M-215, M-350 (the above are manufactured by Toagosei); NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above It is manufactured by Shinnakamura Chemical Industry); SPC-1000, SPC-3000 (the above are manufactured by Showa Denko), etc.

In order to use radicals or alkalis as the starting species, rapid reaction progress or excellent curability, a polymerizable composition combining any one of the following (1) to (5) is preferred. Higher, the combination of (2) is preferred. In order to lower the curing temperature, the combination of (4) is preferred. Furthermore, in order to obtain two characteristics, epoxy resin, ethylenically unsaturated compound and All thiol compounds are included. (1) A polymerizable composition containing the polymerization initiator of the present invention and an epoxy resin. (2) A polymerizable composition containing the polymerization initiator of the present invention and an ethylenically unsaturated compound. (3) A polymerizable composition containing the polymerization initiator of the present invention, epoxy resin and phenol resin. (4) A polymerizable composition containing the polymerization initiator of the present invention, an epoxy resin, and a thiol compound. (5) A polymerizable composition containing the polymerization initiator of the present invention, an ethylenically unsaturated compound, and a mercaptan compound.

The content of the polymerizable compound may be an appropriate amount according to the purpose of use. In order to prevent poor curing, it is preferable to contain 50 parts by mass or more of the solid components (all components except the solvent) in the polymerizable composition. It is more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. Particularly when the polymerizable composition of the present invention contains epoxy resin, as its preferred amount, in order to exhibit curability or adhesiveness, it is preferably 10 mass of the components other than the solvent in the composition % Or more and 90 mass% or less, more preferably 30 mass% or more and 70 mass% or less. Especially when the polymerizable composition of the present invention contains an ethylenically unsaturated compound, as its preferred amount, in terms of curability or initial curability, among the components other than the solvent in the composition, it is more It is preferably 10% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. Especially in the case where the polymerizable composition of the present invention contains a thiol compound, as its preferred amount, in terms of curability or reactivity, 10 of the components other than the solvent in the composition are preferred. Mass% or more and 60 mass% or less, more preferably 20 mass% or more and 50 mass% or less.

In the polymerizable composition of the present invention, additives such as inorganic compounds, colored materials, latent epoxy curing agents, chain transfer agents, sensitizers, and solvents can be used 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 oxide, and aluminum oxide; layered clay minerals, rice Lori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate , Calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds can be used as fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, etc., for example.

Examples of the above-mentioned colored materials include pigments, dyes, and natural pigments. These colored materials can be used alone or in a mixture of two or more.

As the above-mentioned pigments, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds; dibenzopyran compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; Indolinone compound; isoindoline compound; quinacridone compound; anthrenanthrone compound; pyrenone compound; perylene compound; dione pyrrolopyrrole compound; thioindigo compound; Methane compounds; Quinophthalone compounds; Naphthalenetetracarboxylic acid; Metal complex compounds of azo dyes and cyanine dyes; Lake pigments; Carbon black, or acetylene black, obtained by furnace method, channel method or thermal method Carbon black such as Ketjen black or lamp black; the above-mentioned carbon black is adjusted or coated with epoxy resin, the above-mentioned carbon black is preliminarily treated with resin dispersion in a solvent and adsorbed 20-200 mg/g of resin, the above Carbon black is formed by acidic or alkaline surface treatment, with an average particle size of 8 nm or more and a DBP (Dibutyl phthalate) oil absorption of 90 ml/100 g or less, according to 950℃ Carbon black with a total oxygen content of 9 mg or more per 100 m ² surface area calculated by CO and CO ₂ in the volatiles below; 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, Milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, Organic or inorganic pigments such as iron blue, ultramarine blue, sky blue, dark green, emerald green, lead sulfate, yellow red, zinc yellow, iron red (iron oxide red (III)), cadmium red, synthetic iron black, umber, etc. 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.

Examples of the above-mentioned dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, dibenzopyran dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, Dyes such as quinoline dyes, nitro dyes, indamine dyes, phthalocyanine dyes, cyanine dyes, etc., can be used in combination of plural kinds.

As the above-mentioned latent epoxy curing agent, for example, dicyandiamide, modified polyamine, hydrazine, 4,4'-diaminodiphenylsulfonate, boron trifluoride amine complex salt, imidazole , Guanamines, imidazoles, ureas and melamine, etc.

、二異丙基-9-氧硫𠮿

、下述化合物No.C1、三(2-羥乙基)異氰尿酸酯三巰基丙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 compound containing a sulfur atom is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionic acid) Amino 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-methylthio)phenyl ether, 2-mercapto Ethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzo Mercapto compounds such as imidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 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 Tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexamethylenedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol disulfide Propionate, Butanediol Dithioglycolate, Ethylene Glycol Dimercaptoacetate, Trimethylolpropane Trimercaptoacetate, Butanediol Dithiopropionate, Trimethylolpropane Three Thiopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trithiopropionate, diethyl-9-oxy Sulfur

, Diisopropyl-9-oxysulfur 𠮿

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

[化25]

The above-mentioned solvent means a compound that is not classified as a compound of the present invention, a polymerizable compound, which is liquid at 25°C and 1 atmosphere, and can usually dissolve the above-mentioned components (polymerization initiator (A), polymerizable compound (B), etc.) Or dispersed compounds. As the solvent, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2- Ketones such as heptanone; ether solvents such as diethyl ether, diethane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, Ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, TEXANOL, etc.; lactone solvents such as γ-butyrolactone ; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other cellosolve solvents; methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, pentanol and other alcoholic solvents; ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, propionic acid Ether ester solvents such as ethoxyethyl; BTX (Benzene-Toluene-Xylene) solvents such as benzene, toluene, and xylene; Fats such as hexane, heptane, octane, and cyclohexane Group hydrocarbon solvents; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; mineral spirits, Swazol#310 (Kosmo Songshan Petroleum Co., Ltd.), Solvesso#100 (Exxon Chemical Co., Ltd.), etc. Alkane solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents ; Aniline, triethylamine, pyridine, N,N-dimethylformamide, N-methylpyrrolidone and other alkaline solvents; acetic acid; acetonitrile; carbon disulfide; dimethyl sulfide; water, etc., such solvents One type can be used, or it can be used as a mixed solvent of two or more types. Among them, in terms of alkaline developability, patterning properties, film forming properties, solubility, and handling properties, ketones, lactone-based solvents, ether ester-based solvents, or alkaline solvents are preferably used, and particularly preferably Propylene glycol-1-monomethyl ether-2-acetate (hereinafter, also referred to as "PGMEA"), cyclopentanone, cyclohexanone, γ-butyrolactone, and dimethylformamide were used. In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, as long as the components are uniformly dispersed or dissolved, and the polymerizable composition of the present invention exhibits a liquid or slurry state suitable for each application. In general, it is preferable to contain the solvent in the amount of the solid content (all components except the solvent) in the polymerizable composition of the present invention within the range of 10 to 98% by mass.

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. Compounds, (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, polyurethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, etc. When the above-mentioned organic polymer is used, its content is preferably 10 to 500 parts by mass relative to 100 parts by mass of the polymerizable compound (B).

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

As the above-mentioned surfactants, fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic-based surfactants such as higher fatty acid alkali metal salts, alkyl sulfonates, and alkyl sulfates can be used. Surfactants; cationic surfactants such as higher amine hydrohalides and quaternary ammonium salts; polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, monoglycerin fatty acid esters Surfactants such as nonionic surfactants; amphoteric surfactants; surfactants such as silicone-based surfactants can 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 and the like having isocyanate groups, methacrylic groups or epoxy groups are suitably used. Silane coupling agent.

As the above-mentioned melamine compound, all or a part (at least 2) of the active methylol group (CH ₂ OH group) in the nitrogen compound can be exemplified by alkyl etherification, such as: (poly) methylol melamine, ( Poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea, etc. Here, as the alkyl group constituting the alkyl ether, a methyl group, an ethyl group, or a butyl group may be mentioned, and they may be the same or different. In addition, the methylol group that has not been etherified with the alkyl group may undergo self-condensation within one molecule, or may undergo condensation 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 the polymerizable composition, alkyl etherified melamines 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) (except inorganic compounds, colored materials, and solvents) can be appropriately selected according to the purpose of use. There is no restriction|limiting in particular, Preferably it is 50 mass parts or less in total with respect to 100 mass parts of polymerizable compounds (B).

The polymerizable composition of the present invention can be irradiated with energy rays to form a cured product. The hardened material is formed in an appropriate shape according to the application. For example, in the case of forming a film-like cured product, the polymerizable composition of the present invention can be used with a spin coater, roll coater, bar coater, die nozzle coater, curtain coater, Various known methods 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 applied to a supporting substrate such as a film, and then transferred to another supporting substrate, and the application method is not limited.

As the light source of the energy line used to harden the polymerizable composition of the present invention, 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 can be used. Object lamps, fluorescent lamps, tungsten filament lamps, excimer lamps, germicidal lamps, light-emitting diodes, electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from CRT (cathode-ray tube) light sources, etc. , Or high-energy rays such as electron beam, X-ray, radiation, etc., in order to achieve excellent curability, it is better to use ultra-high pressure mercury lamp, mercury vapor arc lamp, carbon arc lamp, xenon arc lamp that emits light with a wavelength of 300-450 nm Wait.

Furthermore, the direct laser engraving method uses laser light as an exposure light source without using a mask, and directly forms an image based on digital information from a computer, etc., which not only improves productivity, but also improves resolution or position accuracy, etc., so it is useful As the laser light, it is suitable to use light with a wavelength of 340 ~ 430 nm. Excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductors can also be used Lasers and YAG (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 the visible light to infrared light in order to make it excellent in curability.

In addition, with regard to the curing of the polymerizable composition of the present invention, heating is usually required after the above-mentioned energy rays are irradiated. In terms of curability, heating is preferably performed at about 40 to 150°C.

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 (Pesonal Computer, personal computer) displays, Color filters in liquid crystal display elements for color displays such as portable information terminals and digital cameras; color filters in 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; The photoresist used for color filters or plasma display panels, electroluminescent display devices, and LCD (Liquid Crystal Display, liquid crystal display device) manufacturing steps used to form the structure of the photoresist; Encapsulated electrical and electronic components; solder resist; magnetic recording materials; small mechanical parts; waveguides; optical switches; coating masks; etching masks; color test systems; glass fiber cable coatings; screen printing Templates; materials used to produce three-dimensional objects by stereo lithography; materials for holographic recording; image recording materials; micro-electronic circuits; decolorizing materials; decolorizing materials for image recording materials; images using microcapsules Decolorizing materials for recording materials; photoresist materials for printed wiring boards; photoresist materials for UV (ultraviolet) and visible laser direct imaging systems; photoresists for forming dielectric layers when successively stacking printed circuit boards The use of the material or protective film is not particularly limited.

The polymerizable composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and the purpose of forming protrusions for vertical alignment type liquid crystal display elements. In particular, it can be used 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) pairing with a mask having a specific pattern shape The step of irradiating the coating with energy rays (light); (3) the baking step after exposure; (4) the step of developing the exposed coating; (5) the step of heating the developed coating.

The polymerizable composition of the present invention to which a colored material is added is suitably used as a photoresist for forming each pixel such as RGB in a color filter, or a photoresist for a black matrix forming a partition wall of each pixel. Furthermore, when a photoresist for a black matrix of an ink-repellent agent is added, it is preferably used for a partition wall for an inkjet color filter having a contour angle of 50° or more. As the ink repellent, a fluorine-based surfactant and a composition containing the fluorine-based surfactant are suitably used.

When used in 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 transfer body, and the 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 A partition wall that separates 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 is used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable supporting substrate. The laminate can be developed with an alkaline aqueous solution. In order to achieve an excellent balance between insulation and curability, the thickness of the insulating resin layer is preferably 10 to 100 μm.

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

Hereinafter, the present invention will be described in more 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.

[Production Example 1] Synthesis of oxime body 1 Add 1-(9-ethyl-6-(2-methyl-2-morpholinopropionyl)-9H-carbazole-3 to a 100 ml four-necked flask -Base) octane-1-one 1.0 eq. and dissolved in dimethylformamide (300% by weight of theoretical yield). 1.05 eq. of 4 M·HCl-ethyl acetate and 1.1 eq. of isobutyl nitrite were added thereto, and the mixture was stirred at 45° C. for 1 hour. Methyl isobutyl ketone was added to the reaction liquid, and after washing with ion-exchanged water three times, it was dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent=ethyl acetate:hexane=volume ratio 1:1). In this way, the target product as a yellow solid compound was obtained with a yield of 70%. [化25A]

[Manufacturing Example 2] Synthesis of oxime 2 To a 100 ml four-necked flask was added 2-(6-(3-cyclohexylpropionyl)-9-ethyl-9H-carbazol-3-yl)-2- 1.0 eq. of ethyl oxoacetate, and dissolved in dimethylformamide (300% by weight of theoretical yield). 1.05 eq. of 4M·HCl-ethyl acetate and 1.1 eq. of isobutyl nitrite were added thereto, and the mixture was stirred at 45°C for 1 hour. Methyl isobutyl ketone was added to the reaction liquid, and after washing with ion-exchanged water three times, it was dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent=ethyl acetate:hexane=volume ratio 3:7). In this way, the target product as a yellow solid compound was obtained with a yield of 60%. [化26]

[Production Example 3] Synthesis of oxime 3 To a 100 ml four-necked flask, 1.0 eq. of methyl 2-(7-octanyl-9H-茀-2-yl)-2-oxoacetate was added and dissolved in Dimethylformamide (500% by weight of the theoretical yield), and obtain a solution. To the obtained solution, 2.2 eq. of hydroxylammonium chloride and 2.2 eq. of pyridine were added, and the mixture was heated and stirred at 60°C for 8 hours to obtain a reaction mixture. Ion-exchanged water was added to the reaction mixture, and extraction was performed with chloroform. The organic layer was washed twice with ion-exchanged water, and dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent=hexane:ethyl acetate=volume ratio 90:10) to obtain oxime body 3 as a light yellow powdery compound with a yield of 30%. [化26A]

[Example 1] Synthesis of compound 1 To a 100 ml four-necked flask were added 1.0 eq. of oxime 1, dichloromethane (500% by weight of the theoretical yield), and 2.0 eq. of triethylamine, on an ice bath at 5°C Stir under. Dissolving 1.1 eq. of 4-nitrophenyl chloroformate in dichloromethane was added dropwise. After the dropwise addition, it was stirred at room temperature for 30 minutes. After cooling to 5°C on an ice bath again, piperidine 1.1 eq. was added dropwise. It was stirred at 45°C for 7 hours, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and after washing with ion-exchanged water twice, it was concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate: hexane = volume ratio 1:3). Crystallization was performed with acetonitrile to obtain the target compound as a pale yellow powdery compound with a yield of 37%. The obtained compound was subjected to TG-DTA (Thermogravimetry-Differential Thermal Analysis) (melting point) and ¹ H-NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) analysis. The results are shown in [Table 1] and [Table 2].

[化27]

[Example 2] Synthesis of compound 2 Except for changing the oxime body 1 described in Example 1 to the oxime body 2, the same operation as in Example 1 was performed until the water washing step. The concentrated residue was purified by silica gel column chromatography (eluent: ethyl acetate: hexane = volume ratio 3:7) to obtain the target compound as a yellow viscous liquid compound with a yield of 50%. The obtained compound was analyzed by TG-DTA (melting point) and ¹ H-NMR. The results are shown in [Table 1] and [Table 2].

[化28]

[Example 3] Synthesis of compound 3 To a 100 ml four-necked flask, 1.0 eq. of oxime body 3, 1.0 eq. of chloroform (500% by weight of the theoretical output), and 2.0 eq. of triethylamine were added, and carried out on an ice bath at 5°C. Stir. To this, 1.1 eq. of 4-nitrophenyl chloroformate was dissolved in chloroform (500% by weight of the theoretical output). After the dropwise addition, it was stirred at room temperature for 1 hour. After cooling to 5°C on an ice bath again, 1.1 eq. of dibutylamine was added dropwise. After stirring for 3 hours at room temperature, it was washed 3 times with a 1% by mass aqueous sodium hydroxide solution and 3 times with ion-exchanged water, and the organic layer was dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent=hexane:ethyl acetate=volume ratio 95:5) to obtain compound 3 as a yellow amorphous solid compound with a yield of 25%. The obtained compound was ^{analyzed by 1} H-NMR, and the result is shown in [Table 2A]. [化28A]

[Table 1] Compound melting point measurement data Compound name Melting point (℃) Example 1 Compound 1 189 Example 2 Compound 2 -(Liquid)

[Table 2] ¹ H-NMR measurement data of the compound Chemical shift/ppm (multiplicity, number of protons) Compound 1 (DMSO-d ₆ , 400 MHz) 9.71 (d, 1H), 9.03 (d, 1H), 8.71 (dd, 1H), 8.40 (dd, 1H), 7.46 (d, 1H), 7.41 (d, 1H), 4.40 (q, 2H), 3.74 (t, 4H), 3.60-3.52 (m, 4H), 2.80 (d, 2H), 2.68 (t, 4H), 1.83-1.55 (m, 12H), 1.48 (t, 3H), 1.42 (s, 6H) ), 1.29-1.01 (m, 5H) Compound 2 (CDCl ₃ , 400 MHz) 8.97 (d, 1H), 8.83 (d, 1H), 8.40 (dd, 1H), 8.19 (dd, 1H), 7.48 (dd, 2H), 4.53 (q, 2H), 4.41 (q, 2H), 3.62 -3.52 (m, 4H), 2.82 (t, 2H), 1.73-1.16 (m, 23H)

[Table 2A] ¹ H-NMR measurement data of compound 3 Chemical shift/ppm (multiplicity, number of protons) Compound 3 (CDCl ₃ , 400 MHz) 8.15-8.05 (m, 3H), 8.00 (d, 1H), 7.95-7.90 (m, 2H), 4.12 (s, 2H), 3.61 (s, 3H), 2.94 (t, 4H), 2. 70 (t, 2H), 1.50-1.25 (m, 18H), 0.95-0.85 (m, 9H)

[Example 1 and Comparative Examples 1 and 2] Preparation of photosensitive composition The formulation was performed as described in [Table 3], and photosensitive composition 1 and comparative photosensitive compositions 1 and 2 were obtained. 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. The structure of part of the following ingredients is shown below.

A-1: Compound 1 A'-2: 1-(4-((4-nitrophenyl)thio)phenyl)-2-(((piperidin-1-carbonyl)oxy)imino)dodecane-1 -Ketone (carboxamide type photobase generator) A'-3: Omnirad819 (manufactured by IGM Resins) B: Dipentaerythritol hexaacrylate (Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.) C: EP-4100E (manufactured by ADEKA) D: Pentaerythritol-tetrakis (3-mercaptobutyrate) (PE-1, manufactured by Showa Denko) E: N,N-dimethylformamide

[化29]

[Evaluation 1] Adhesion to a substrate (curability) As an adhesive, the compositions of the respective examples and comparative examples were used, and the evaluation was carried out in the following procedure. Prepare two substrates made of SUS (Steel Use Stainless) with a rectangular shape of 25 mm in length × 50 mm in width × 2 mm in thickness. One of the two short sides in the longitudinal direction of one substrate is about 20 mm from one of the short sides to the other short side (the part of 25 cm in length × about 20 cm in width), using a bar coater to prepare membrane. It was irradiated with a mercury high-pressure lamp at 1,000 mJ/cm ^2. After that, another substrate was attached and fixed with a jig. In this state, it was heated in an oven at 100°C for 1 hour, and left to cool at room temperature 25°C for 30 minutes. It was confirmed whether the two SUS substrates could be peeled off at this time, and for those that could not be peeled off, it was judged that they were sufficiently cured and adhered. The results are shown in [Table 3].

[Evaluation 2] The initial curability was formed on a SUS substrate using a bar coater to form a film of the compositions of the respective examples and comparative examples, and irradiated ^{with a mercury high-pressure lamp at 500 mJ/cm 2.} Perform contact diagnosis on the irradiated sample to confirm whether it is sticky and sticky. The results are shown in [Table 3]. In the adhesive application, from the viewpoint of bonding, it is best to increase the viscosity of the composition, and secondly, it is preferable to have no change and no adhesion in order. In the case of increased adhesion during lamination, the position accuracy of the lamination is improved, but in the case of no change, the position accuracy is lacking, and the non-adhesive ones cannot be connected.

[table 3] Example 1 Comparative example 1 Comparative example 2 Initiator A-1 1.0 - - A'-2 - 1.0 - A'-3 - - 1.0 Radical polymerizable ingredients B 12.2 12.2 12.2 Epoxy composition C 48.8 48.8 48.8 Mercaptan D 35.1 35.1 35.1 Solvent E 2.9 2.9 2.9 Evaluation Continuity then then Can't be followed Initial hardening Stickiness No change Not sticky

It is confirmed from the results in Table 3 that when the compound of the present invention is used, when a radical polymerizable component is used in combination, the initial curability is improved without the need to add a photo-radical polymerization initiator. In addition, it was confirmed that when the compound of the present invention is used, when an anionic curable component (epoxy component, thiol component) is used, curing proceeds to the extent that adhesiveness is exhibited. From this, it can be seen that only the compound of the present invention can exhibit the performance of both a photoradical polymerization initiator and a photobase generator, while simultaneously using an anionic curable component (epoxy component, thiol component) and radical polymerizability. In the case of the ingredients, a cured product with high initial curability and excellent adhesion to the substrate can be obtained. Obviously, a single initiator component can cause a hardening reaction between an anionic hardening component and a radical polymerizable component, and the compound of the present invention is excellent as a polymerization initiator that can harden various compositions.

Claims (10)

A carbamethoxime compound, which has a group represented by the following general formula (I) in the same molecule and a photo-radical generating group that does not have a carbamate group: [化1]

(In the formula, R ¹ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, a heterocyclic group with 2 to 20 carbon atoms, or the hydrocarbon group or the heterocyclic group One or two or more of the hydrogen atoms are substituted with a monovalent group selected from the following group I, or it means that the hydrocarbon group, the heterocyclic group, or the like is substituted with a group selected from the group I One or two or more of the methylene groups in the resulting group are substituted with divalent groups selected from the following group II, X ¹ represents -NR ² R ³ , or the following general formula (a ) Or a group represented by the following general formula (b), R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or one or more of the hydrogen atoms in the hydrocarbon group is substituted A group formed from a monovalent group in the following group I, or means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group is substituted with a group selected from the group I are substituted The group formed from the divalent group of the following group II, R ² and R ³ may be connected to each other to form a carbon atom ring containing a hydrogen atom, a nitrogen atom and a carbon atom, or a hydrogen atom, an oxygen atom , Nitrogen atom and carbon atom ring with 2-10 carbon atoms, Group I is halogen atom, cyano group, nitro group, hydroxyl group, -OR ⁴ , -COOR ⁴ , -CO-R ⁴ or -SR ⁴ , R ⁴ It represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a group with 1 to 20 carbon atoms in which one or more of the hydrogen atoms in the hydrocarbon group is substituted by a halogen atom, a cyano group, a nitro group or a hydroxyl group, Or it means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group substituted by a halogen atom, a cyano group, a nitro group or a hydroxyl group are substituted with a divalent group selected from the following group II When there are multiple R ⁴ in the base, they can be the same or different. Group II is -O-, -CO-, -COO-, -OCO-, -NR ⁵ -, -NR ⁵ CO- and -S-, R ⁵ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R ⁵ in the group, they may be the same or different. n represents 0 or 1, *Indicates a bond key) [化2]

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or One or more of the hydrogen atoms in the hydrocarbyl group is substituted with a monovalent group selected from the above group I, or it means the hydrocarbyl group or the hydrocarbyl group is substituted with a group selected from the group I One or more of the methylene groups are substituted with divalent groups selected from the above group II, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be independently connected to each other to form a ring with 2 to 10 carbon atoms containing hydrogen, nitrogen, and carbon atoms, or a ring containing hydrogen, oxygen, nitrogen, and carbon atoms. A ring with 2 to 10 carbon atoms, * indicates a bonding bond). The amine methyl oxime compound of claim 1, which has the structure represented by the following general formula (II): [化3]

(In the formula, A ¹ represents an aromatic ring structure having 6 to 20 carbon atoms, R ³¹ represents a group represented by the above general formula (I), R ³² represents a photo radical generating group without a carbamate group, A hydrocarbon group with 1 to 20 carbon atoms substituted by a photo-radical generating group without a carbamate group, and a carbon number of 2 to substituted by a photo radical generating group without a carbamate group 20 of the heterocyclic group, or one or more of the hydrogen atoms in the hydrocarbon group or the heterocyclic group is substituted with a group selected from the following group III monovalent groups, or represents the hydrocarbon group, One or two or more of the methylene groups in the heterocyclic group or the group in which the heterocyclic group is substituted with a group selected from group III are substituted with a divalent group selected from the following group IV , R ³³ each independently represents a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, a heterocyclic group with 2 to 20 carbon atoms, or a hydrogen atom in the hydrocarbon group or the heterocyclic group One or two or more of them are substituted with a group selected from the following group III monovalent group, or it means that the hydrocarbon group, the heterocyclic group, or the like is substituted with a group selected from group III One or two or more of the methylene groups in the group are substituted with divalent groups selected from the following group IV. Group III is a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ³⁴ ,- COOR ³⁴ , -CO-R ³⁴ or -SR ³⁴ , R ³⁴ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or one or more of the hydrogen atoms in the hydrocarbon group is replaced by a halogen atom, a cyano group, a nitro group, or A group with 1 to 20 carbon atoms substituted by a hydroxy group, or means that one or more of the methylene groups in the hydrocarbyl group or the hydrocarbyl group substituted by a halogen atom, a cyano group, a nitro group, or a hydroxy group Substitution is a group formed by a divalent group selected from the above group IV. When there are plural R ³⁴ in the group, they may be the same or different. Group IV is -O-, -CO-, -COO -, -OCO-, -NR ³⁵ -, -NR ³⁵ CO- or -S-, R ³⁵ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and when there are more than one R ³⁵ in the group, etc. May be the same or different, a represents an integer of 1-19, when a is an integer of 2 or more, there ^{may be a plurality of R 31} which may be the same or different, b represents an integer of 1-19, where b is In the case of an integer of 2 or more, a plurality of R ³² may be the same or different, and c represents an integer from 0 to 18. When c is an integer of 2 or more, there ^{may be a plurality of R 33 that} may be the same, also Can be different, a+b+c is 20 or less). The amine methyl oxime compound of claim 2, wherein A ¹ is a structure represented by the following general formula (III): [化4]

(In the general formula (III), Y ¹ represents oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , Y ² represents single bond, no bond, oxygen atom, sulfur atom, selenium atom , CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, and a heterogeneous group with 2 to 20 carbon atoms One or more of the hydrogen atoms in the cyclic group, the hydrocarbon group, or the heterocyclic group is substituted with a monovalent group selected from the following group V, or it represents the hydrocarbon group or the heterocyclic group Or a group in which one or more of the methylene groups in a group substituted by a group selected from group V are substituted with -O- or -CO-, group V is a halogen atom or a nitro group , Cyano group, hydroxyl group, carboxyl group or a heterocyclic group containing 2-20 carbon atoms). The carbamate compound of claim 1 or 2, wherein the photo radical generating group without carbamate group is the following general formula (IVa), (IVb), (IVc), (IVd), ( The base represented by IVe), (IVf) or (IVg): [化5]

(In the general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf) and (IVg), R ⁵¹ represents OR ⁸¹ , NR ⁸² R ⁸³ or a carbon number of 2-20 Containing a heterocyclic group, R ⁵² and R ⁵³ each independently represent R ⁸¹ or OR ⁸¹ , R ⁵² and R ⁵³ may bond to form a ring, R ⁸¹ , R ⁸² and R ⁸³ each independently represent a hydrogen atom or the number of carbon atoms A hydrocarbon group of 1-20, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ and R ⁷¹ represent an aryl group with 6 to 20 carbon atoms, R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ and R ⁶⁷ each independently represent an aryl group having 6 to 20 carbon atoms or a single bond, R ⁶⁸ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ⁶⁹ and R ⁷⁰ each independently represent R ⁸¹ or OR ⁸¹ , * means a bonding key). A potential alkali generator, which contains the carbamate compound according to any one of claims 1 to 4. A polymerization initiator containing the carboxamide compound according to any one of claims 1 to 4. A polymerizable composition containing the carbamate compound and polymerizable compound according to any one of claims 1 to 4. Such as the polymerizable composition of claim 7, which is any combination of the following (1) to (5): (1) Polymerizable composition containing the polymerization initiator and epoxy resin of claim 6 (2) A polymerizable composition containing the polymerization initiator of claim 6 and an ethylenically unsaturated compound (3) Polymerizable composition containing polymerization initiator, epoxy resin and phenol resin as in claim 6 (4) Polymerizable composition containing polymerization initiator, epoxy resin and thiol compound as claimed in claim 6 (5) A polymerizable composition containing the polymerization initiator of claim 6, an ethylenically unsaturated compound, and a mercaptan compound. A hardened product obtained from the polymerizable composition of claim 7 or 8. A method for manufacturing a hardened product, which has the step of irradiating the polymerizable composition of claim 7 or 8 with energy rays.