JP2016079158A - New polymerization initiator and radical polymerizable composition containing polymerization initiator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound which is superior in stability, has low sublimability, and is useful as a high sensitive polymerization initiator absorbing near ultra violet light such as 365 nm and being activated, and a polymerization initiator using the compound.SOLUTION: A compound shown in a following general formula (I) and a polymerization initiator containing the compound. The polymerization initiator can be used suitably as a polymerization initiator of a radical polymerizable composition containing a polymerizable compound having ethylenic unsaturated bonding.SELECTED DRAWING: None

Description

  The present invention relates to a novel polymerization initiator having an α-aminoalkylphenone skeleton and a radical polymerizable composition comprising the polymerization initiator containing a polymerizable compound having an ethylenically unsaturated bond.

  The radically polymerizable composition is a composition obtained by adding a polymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by heating or irradiation with energy rays. It is used for various photoresists.

As a polymerization initiator used in the radical polymerizable composition, Patent Document 1 below discloses a photopolymerizable composition using an α-aminoalkylphenone derivative as a photopolymerization initiator. 3 discloses a novel α-aminoacetophenone photoinitiator.
However, the α-aminoalkylphenone derivatives described in Patent Documents 1 to 3 are not sufficiently low in sublimation property, causing a photomask or a heating furnace to be contaminated by a sublimation product.

Japanese Patent Application Laid-Open No. 10-069079 JP-A-10-291969 CN101941952 Specification

  The problem to be solved is that there has never been a polymerization initiator with satisfactory sensitivity.

  Accordingly, an object of the present invention is to provide a novel compound useful as a highly sensitive polymerization initiator that is excellent in stability, has low sublimation properties, and efficiently absorbs and activates near-ultraviolet light such as 365 nm. An object of the present invention is to provide a polymerization initiator used and a radically polymerizable composition.

  The present invention achieves the above object by providing a novel compound represented by the following general formula (I) and a polymerization initiator containing the compound.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子；水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数１〜１２のアルキル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換のフェニル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数７〜３０のアリールアルキル基；炭素原子数２〜１２のアルケニル基を表し、Ｒ^１とＲ^２は、それぞれ連結して３〜６員環の複素環を形成していてもよく、
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子；水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数１〜１２のアルキル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換のフェニル基；炭素原子数１〜４のアルキル基、水酸基、炭素原子数１〜４のアルコキシ基、アミノ基、炭素原子数１〜４のアルキルチオ基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数７〜３０のアリールアルキル基；炭素原子数２〜１２のアルケニル基；Ｒ^３とＲ^４は、連結して３〜６員環の環状アルカンを形成してもよく、
Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基；ハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルキル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数７〜３０のアリールアルキル基を表し、
Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、水酸基、カルボキシル基、ハロゲン原子または炭素原子数１〜４のアルキル基を表し、ｎが２以上の場合は同じ又は異なり、
ｎは、１〜１２の数を表し、
Ｘは、二価の有機基であり、
Ｙは、下記式（Ｉ−１）又は（Ｉ−２）で表される構造であり、
上記アルキル基及びアリールアルキル基、ならびにアルキレン基中のメチレン鎖は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−又は−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよい。）

(Wherein R ¹ and R ² are each independently a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or an unsubstituted alkyl group having 1 to 12 carbon atoms; An alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, halogen atoms, an arylalkyl group or unsubstituted having 7 to 30 carbon atoms which is substituted with a cyano group or a nitro group; an alkenyl group having 2 to 12 carbon atoms, R ¹ and R ^2, connected respectively May form a 3- to 6-membered heterocyclic ring,
R ³ and R ⁴ are each independently a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted alkyl group having 1 to 12 carbon atoms; An alkyl group having 4 to 4 alkyl groups, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and 1 to 4 carbon atoms An alkoxy group, an amino group, an alkylthio group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms; 2 to 12 alkenyl groups; R ³ and R ⁴ may be linked to form a 3- to 6-membered cyclic alkane;
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group; an alkyl having 1 to 8 carbon atoms that is substituted or unsubstituted by a halogen atom A group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and when n is 2 or more, they are the same or different,
n represents a number from 1 to 12,
X is a divalent organic group,
Y is a structure represented by the following formula (I-1) or (I-2),
The methylene chain in the above alkyl group and arylalkyl group and alkylene group is replaced with —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O—. It may be done. )

（式中、Ｒ^1’及びＲ^2’は、それぞれ独立に、水素原子；水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数１〜１２のアルキル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換のフェニル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数７〜３０のアリールアルキル基；炭素原子数２〜１２のアルケニル基を表し、Ｒ^１’とＲ^２’は、それぞれ連結して３〜６員環の複素環を形成していてもよく、
Ｒ^３’及びＲ^４’は、それぞれ独立に、水素原子；水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数１〜１２のアルキル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換のフェニル基；炭素原子数１〜４のアルキル基、水酸基、炭素原子数１〜４のアルコキシ基、アミノ基、炭素原子数１〜４のアルキルチオ基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数７〜３０のアリールアルキル基；炭素原子数２〜１２のアルケニル基を表し、Ｒ^３’とＲ^４’は、連結して３〜６員環の環状アルカンを形成してもよく、
Ｒ^５’、Ｒ^６’、Ｒ^７’及びＲ^８’は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基；ハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルキル基；炭素原子数１〜４のアルキル基、水酸基、カルボキシル基、ハロゲン原子、シアノ基若しくはニトロ基で置換されているかあるいは無置換の炭素原子数７〜３０のアリールアルキル基を表し、
上記アルキル基及びアリールアルキル基、ならびにアルキレン基中のメチレン鎖は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−又は−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよい。）

Wherein R ^{1 ′} and R ^{2 ′} are each independently a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or an unsubstituted alkyl group having 1 to 12 carbon atoms. Group: an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group A group, a halogen atom, a cyano group or a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms; an alkenyl group having 2 to 12 carbon atoms, wherein R ^{1 ′} and R ^{2 ′} are , Each may be linked to form a 3- to 6-membered heterocyclic ring,
R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted alkyl group having 1 to 12 carbon atoms; a carbon atom An alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and 1 to 1 carbon atoms 4 alkoxy groups, amino groups, alkylthio groups having 1 to 4 carbon atoms, carboxyl groups, halogen atoms, cyano groups, nitro groups, or unsubstituted arylalkyl groups having 7 to 30 carbon atoms; carbon Represents an alkenyl group having 2 to 12 atoms, R ^{3 ′} and R ^{4 ′} may be linked to form a 3- to 6-membered cyclic alkane;
R ^{5 ′} , R ^{6 ′} , R ^{7 ′,} and R ^{8 ′} each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group; a halogen atom-substituted or unsubstituted carbon atom of 1 An alkyl group having ˜8; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms ,
The methylene chain in the above alkyl group and arylalkyl group and alkylene group is replaced with —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O—. It may be done. )

（式中、Ｒ^１２及びＲ^１３は、それぞれ独立に、水素原子、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ^２２、ＯＲ^２３、ＳＲ^２４、ＮＲ^２５Ｒ^２６、ＣＯＲ^２７、ＳＯＲ^２８、ＳＯ_２Ｒ^２９又はＣＯＮＲ^３０Ｒ^３１を表し、Ｒ^１６及びＲ^１８は、互いに結合して環を形成していてもよく、
Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０及びＲ^３１は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｘ^２は、単結合又はＣＯを表し、
Ｘ^３は、酸素原子、硫黄原子、セレン原子、ＣＲ^３２Ｒ^３３、ＣＯ、ＮＲ^３４又はＰＲ^３５を表し、
Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^１２、Ｒ^１３、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５中の炭素原子数１〜２０のアルキル基又は炭素原子数７〜３０のアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環基で置換されていてもよく、該アルキル基又はアリールアルキル基中のメチレン鎖は−Ｏ−で中断されていてもよい。）

Wherein R ¹² and R ¹³ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ²² , OR ²³ , SR ²⁴ , NR ²⁵ R ²⁶ , COR ²⁷ , SOR ²⁸ , SO ₂ R ²⁹ or CONR ³⁰ R ³¹ , R ¹⁶ and R ¹⁸ may be bonded to each other to form a ring,
R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents a single bond or CO,
X ³ represents an oxygen atom, a sulfur atom, a selenium atom, CR ³² R ³³ , CO, NR ³⁴ or PR ³⁵ ,
R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. Represents a heterocyclic group of formula 2 to 20,
Carbons in R ¹² , R ¹³ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ The methylene group in the alkyl group having 1 to 20 atoms or the arylalkyl group having 7 to 30 carbon atoms may be substituted with a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group or heterocyclic group, The methylene chain in the alkyl group or arylalkyl group may be interrupted by -O-. )

  Moreover, this invention provides the radically polymerizable composition formed by making the said polymerization initiator contain the polymeric compound which has an ethylenically unsaturated bond.

  Moreover, this invention provides the hardened | cured material formed by irradiating an energy ray to the said radically polymerizable composition.

  The compound of the present invention has excellent stability and low sublimation, and generates radicals efficiently with respect to emission lines such as 365 nm (i-line) and is useful as a polymerization initiator used in a radically polymerizable composition. It is.

  Hereinafter, the compound of the present invention and the polymerization initiator containing the compound will be described in detail based on preferred embodiments.

  The compound of the present invention is a novel compound represented by the above general formula (I).

R ¹ , R ² , R ³ and R ^{4 in} the general formula (I), and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the formula (I-1) Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.
R ¹ , R ² , R ³ and R ^{4 in} the general formula (I), and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the formula (I-1), As the alkyl group having 1 to 12 carbon atoms substituted with a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, a part or all of the alkyl group having 1 to 12 carbon atoms may be a hydroxyl group or a carboxyl group. And those substituted with a group, a halogen atom, a cyano group or a nitro group.

R ⁵ , R ⁶ , R ⁷ and R ^{8 in the} above general formula (I) and carbon atoms represented by R ^{5 ′} , R ^{6 ′} , R ^{7 ′} and R ^{8 ′} in the above formula (I-1) Examples of the alkyl group having 1 to 8 include those having 1 to 8 carbon atoms among those exemplified as the unsubstituted carbon atoms having 1 to 12 above.
R ⁵ , R ⁶ , R ⁷ and R ^{8 in the} general formula (I) and halogen atoms represented by R ^{5 ′} , R ^{6 ′} , R ^{7 ′} and R ^{8 ′} in the formula (I-1) Examples of the alkyl group having 1 to 8 carbon atoms that is substituted with the above include those in which a part or all of the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom.

R ¹² , R ¹³ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ^{33 in the} above formula (I-2) Examples of the alkyl group having 1 to 20 carbon atoms represented by R ³⁴ and R ³⁵ include nonadecyl and adamantyl in addition to those exemplified as the alkyl group having 1 to 12 carbon atoms.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 in} the above general formula (I), R ^{1 ′} , R ^{2 ′} in the above formula (I-1), R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 ′} , R ^{7 ′} and R ^{8 ′} , and R ¹² , R ¹³ , R ²² , R ²³ , R ²⁴ , R in the above formula (I-2) ^The unsubstituted arylalkyl group having 7 to 30 carbon atoms represented by ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.
R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ^{8 in} the above general formula (I), and R ^{1 ′} , R ^{2 ′} , R ^{5 ′} , R in the above formula (I-1) ^{7 to} 30 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group represented by ^{6 '} , R ^7' and R ^{8 '} As the arylalkyl group, part or all of the arylalkyl group having 7 to 30 carbon atoms is substituted with an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, or a nitro group. Are listed.
R ³ and R ⁴ in the general formula (I), and R ^{3 ′} and R ^{4 ′} in the formula (I-1), an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a carbon atom Examples of the alkoxy group having 1 to 4 carbon atoms, amino group, alkylthio group having 1 to 4 carbon atoms, carboxyl group, halogen atom, cyano group or arylalkyl group having 7 to 30 carbon atoms substituted with a nitro group include A part or all of the arylalkyl group having 7 to 30 carbon atoms may be an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an amino group, or a carbon atom having 1 to 4 carbon atoms. Examples thereof include those substituted with an alkylthio group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

R ¹ , R ² , R ³ and R ^{4 in} the general formula (I), and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the formula (I-1) Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1 -Groups such as a decenyl group.

As the 3- to 6-membered heterocyclic ring that can be formed by linking R ¹ and R ² in the general formula (I) and R ^{1 ′} and R ^{2 ′ in the} formula (I-1), For example, a piperidine ring, a piperazine ring, a morpholine ring, a lactam ring and the like are preferable.

As the 3- to 6-membered cyclic alkane that can be formed by linking R ³ and R ⁴ in the general formula (I) and R ^{3 ′} and R ^{4 ′ in the} formula (I-1), For example, a cyclopentane ring, a cyclohexane ring, etc. are mentioned preferably.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 in} the general formula (I), and R ^{1 ′} and R ^{2 in the} formula (I-1) Examples of the halogen atom that may be substituted for ^' , R ^3' , R ^{4 '} , R ^5' , R ^{6 '} , R ^7' and R ^{8 '} include fluorine, chlorine, bromine and iodine. The halogen atom represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ in the above formula (I-2) includes fluorine, chlorine, bromine and iodine. Is mentioned.

R ¹² , R ¹³ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ^{33 in the} above formula (I-2) The aryl group having 6 to 30 carbon atoms represented by R ³⁴ and R ³⁵ includes phenyl, naphthyl, anthracenyl and the like.

R ¹² , R ¹³ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ^{33 in the} above formula (I-2) Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ³⁴ and R ³⁵ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, and pyrrolidyl. And 5- to 7-membered heterocycles such as imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl and morpholinyl.

In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² in the general formula (I) may be substituted. Examples of the preferable alkyl group having 1 to 4 carbon atoms include those having 1 to 4 carbon atoms among those exemplified as the unsubstituted carbon atoms having 1 to 12 above.

Examples of the alkoxy group having 1 to 4 carbon atoms that may substitute R ³ and R ⁴ , and R ^{3 ′} and R ^{4 ′} in the general formula (I) include methyloxy, chloromethyloxy, Examples include trifluoromethyloxy, cyanomethyloxy, ethyloxy, dichloroethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy and the like.

In addition, R ³ and R ⁴ , and R ^{3 ′} and R ^{4 ′} in the general formula (I) may be substituted, and examples of the alkylthio group having 1 to 4 carbon atoms include methylthio, ethylthio, propylthio, isopropyl Examples include thio, butylthio, sec-butylthio, tert-butylthio and the like.

  Preferred examples of the divalent organic group represented by X in the general formula (I) include the following.

（上記一般式（１）中、Ｘ¹は、単結合、−ＣＲ^３００Ｒ^３１０−、−ＮＲ^３２０−、二価の炭素原子数１〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環基、又は、下記〔化５〕〜〔化７〕で表されるいずれかの置換基を表し、該脂肪族炭化水素基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−、あるいは酸素原子が隣り合うことなしにこれらを組み合わせた結合基で中断されていてもよく、Ｒ^３００及びＲ^３１０は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、＞ＣＯ、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−又は＞ＮＲ^３３０を表し、Ｒ^３２０及びＲ^３３０は、水素原子、置換基を有していてもよい炭素原子数１〜３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６〜３５の芳香族炭化水素基又は置換基を有していてもよい炭素原子数２〜３５の複素環基を表す。）

(In the general formula (1), X ¹ is a single bond, —CR ³⁰⁰ R ³¹⁰ —, —NR ³²⁰ —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or 6 to 35 carbon atoms. An aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, or any substituent represented by the following [Chemical Formula 5] to [Chemical Formula 7], wherein the aliphatic hydrocarbon group is: -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or an oxygen atom may be interrupted by a linking group without combining them, and R ³⁰⁰ and R ³¹⁰ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and Z ¹ and Z ² are each independently , Direct bond, -O-, -S-,> CO, -CO-O-, -O-CO _{, -SO 2 -, - SS -} , - SO- ^or> represents ^{NR 330, R 320} and ^{R 330} is a hydrogen atom, an aliphatic hydrocarbon of good carbon atoms 1 to 35 which may have a substituent Represents an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a group or a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent.

（上記式中、Ｒ^２１０は水素原子、置換基を有していてもよいフェニル基、又は炭素原子数３〜１０のシクロアルキル基を表し、Ｒ^２２０は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有していてもよく、ａは０〜５の整数である。）

(In the above formula, R ²¹⁰ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms, R ²²⁰ represents an alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may have a substituent, and a is 0 to 5 Is an integer.)

（上記式中、Ｒ^２３０及びＲ^２４０は、それぞれ独立に、置換基を有していてもよい炭素原子数１〜１０のアルキル基、置換基を有していてもよい炭素原子数６〜２０のアリール基、置換基を有していてもよい炭素原子数６〜２０のアリールオキシ基、置換基を有していてもよい炭素原子数６〜２０のアリールチオ基、置換基を有していてもよい炭素原子数６〜２０のアリールアルケニル基、置換基を有していてもよい炭素原子数７〜２０のアリールアルキル基、置換基を有していてもよい炭素原子数２〜２０の複素環基又はハロゲン原子を表し、該アルキル基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｒ^２３０は、隣接するＲ^２３０同士で環を形成していてもよく、ｂは０〜４の数を表し、ｃは０〜８の数を表し、ｇは０〜４の数を表し、ｈは０〜４の数を表し、ｇとｈの数の合計は２〜４である。

(In the above formula, R ²³⁰ and R ²⁴⁰ are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 to 20 carbon atoms which may have a substituent. An aryloxy group having 6 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, and a substituent. May be an arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a complex having 2 to 20 carbon atoms which may have a substituent. A methylene group in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and R ²³⁰ is a ring between adjacent R ²³⁰ And b is from 0 to 4 C represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, and the total number of g and h is 2 to 4.

  Accordingly, preferred specific examples of the compound of the present invention represented by the above general formula (I) include the following compound Nos. 1-No. 13 is mentioned. However, the present invention is not limited by the following compounds.

  Although the manufacturing method of the compound of this invention represented by the said general formula (I) is not specifically limited, According to the following scheme, it can synthesize | combine by making the carboxylic acid derivative 1 and the alcohol derivative 1 react.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ¹⁰、Ｘ、Ｙ及びｎは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X, Y and n are the same as those in the general formula (I). is there.)

  The novel compound of the present invention described above is useful as a radical polymerization initiator, particularly as a photopolymerization initiator or a thermal polymerization initiator. Moreover, the novel compound of the present invention can also be suitably used as a sensitizer.

  The polymerization initiator of the present invention contains at least one compound of the present invention, and is particularly useful as a polymerization initiator for a polymerizable compound having an ethylenically unsaturated bond. Moreover, content of the compound of this invention in the polymerization initiator of this invention becomes like this. Preferably it is 30-100 mass%, More preferably, it is 50-100 mass%.

  The radically polymerizable composition of the present invention contains the polymerization initiator of the present invention and a polymerizable compound having an ethylenically unsaturated bond as essential components, and may have an ethylenically unsaturated group as an optional component. It contains a combination of components such as a compound having good alkali developability, an inorganic compound, a coloring material, and a solvent.

The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in radically polymerizable compositions can be used. For example, ethylene, propylene, butylene, isobutylene, chloride Unsaturated aliphatic hydrocarbons such as vinyl, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, highmic acid, crotonic acid , Isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω -Carboxy group and hydroxyl group at both ends of carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate of polymer having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.
Among these, a mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, a polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups, an unsaturated one A polymerization initiator containing the compound of the present invention in an ester of a basic acid and a polyhydric alcohol or polyhydric phenol is suitable.
These polymerizable compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance and used as a copolymer. May be.

  The alkali-developable compound that may have an ethylenically unsaturated group is not particularly limited as long as it is soluble in an alkaline aqueous solution. For example, the resin described in JP-A No. 2004-264414 can be used. Can be mentioned.

Examples of the alkali-developable compound that may have an ethylenically unsaturated group include acrylic ester copolymers, phenol and / or cresol novolac epoxy resins, and polyphenyl having a polyfunctional epoxy group. Resin obtained by allowing unsaturated monobasic acid to act on epoxy groups such as methane type epoxy resin, epoxy acrylate resin, epoxy compound represented by the following general formula (III), and polybasic acid anhydride Can be used.
Among these, a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy compound represented by the following general formula (III) and further causing a polybasic acid anhydride to act is preferable.
Moreover, it is preferable that the compound which has the alkali developability which may have the said ethylenically unsaturated bond contains 0.2-1.0 equivalent of unsaturated groups.

（式中、Ｘ¹は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、炭素原子数３〜２０の脂環式炭化水素基、Ｏ、Ｓ、ＳＯ₂、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ又は下記〔化１６〕、〔化１７〕若しくは〔化１８〕で表される基を表し、上記アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＲ⁵⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｍは０〜１０の整数であり、ｍが０で無いときに存在する光学異性体は、どの異性体でもよい。）

(Wherein X ¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO ₂ , SS, SO, CO, OCO or a group represented by the following [Chemical Formula 16], [Chemical Formula 17] or [Chemical Formula 18] is represented, and the alkylidene group may be substituted with a halogen atom, and R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be substituted. Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the above alkyl group or alkoxy group. And the alkenyl group may be substituted with a halogen atom, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.)

（式中、Ｚ³は水素原子、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０
のアルコキシ基により置換されていてもよいフェニル基、又は炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されていてもよい炭素原子数３〜１０のシクロアルキル基を示し、Ｙ¹は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を示し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｄは０〜５の整数である。）

(In the formula, Z ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
A phenyl group which may be substituted by an alkoxy group, or an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms Y ¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group, and alkenyl group May be substituted with a halogen atom, and d is an integer of 0 to 5. )

（式中、Ｙ²及びＺ⁴は、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリールチオ基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリールアルケニル基、ハロゲン原子で置換されていてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｚ⁴は、隣接するＺ⁴同士で環を形成していてもよく、ｐは０〜４の整数を表し、ｑは０〜８の整数を表し、ｒは０〜４の整数を表し、ｓは０〜４の整数を表し、ｒとｓの数の合計は２〜４の整数である。）

Wherein Y ² and Z ⁴ are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. An aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a complex having 2 to 20 carbon atoms that may be substituted with a halogen atom ring group, or a halogen atom, the alkylene moiety in the alkyl group and arylalkyl group, an unsaturated bond, may be interrupted by -O- or -S-, Z ⁴ , May form a ring with the adjacent Z ⁴ each other, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, s is 0 4 represents an integer, and the total number of r and s is an integer of 2 to 4.)

  Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl Acrylate / malate, dicyclopentadiene / malate and the like can be mentioned.

  In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, trialkyl tet Anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 It is preferable that the acid anhydride structure of the polybasic acid anhydride has a ratio of 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

The alkali-developable photosensitive resin composition of the present invention, which is one of the embodiments of the radical polymerizable composition of the present invention, is a polymerization having the polymerization initiator of the present invention and an ethylenically unsaturated bond as essential components. And a compound having an alkali developability which may have an ethylenically unsaturated group, and as an optional component, a combination of components such as an inorganic compound, a coloring material, and a solvent. Among the alkali-developable photosensitive resin compositions of the present invention, those containing a coloring material are also referred to as the colored alkali-developable photosensitive resin compositions of the present invention.
The polymerizable compound having an ethylenically unsaturated bond and the compound having alkali developability which may have an ethylenically unsaturated group may be the same compound or different from each other. Moreover, even if it is individual, 2 or more types may be used together.

  In order to improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention by adjusting the acid value, together with the alkali-developable compound optionally having an ethylenically unsaturated bond, Functional or polyfunctional epoxy compounds can be used. The alkali-developable compound that may have an ethylenically unsaturated bond preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the amount of monofunctional or polyfunctional epoxy compound used. Is preferably selected so as to satisfy the above acid value.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compound No. E1, No. E2 etc. are mentioned.

As the polyfunctional epoxy compound, when one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers are used, a (colored) alkali-developable photosensitive resin composition having better characteristics can be obtained. Is preferable.
As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (III) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

  In the radically polymerizable composition of the present invention, the content of the polymerization initiator of the present invention is not particularly limited, but is preferably 1 with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. -70 mass parts, More preferably, it is 1-50 mass parts, Most preferably, it is 5-30 mass parts.

  In particular, when the radically polymerizable composition of the present invention is a (colored) alkali-developable photosensitive resin composition, the content of the alkali-developable compound that may have an ethylenically unsaturated bond is In the (colored) alkali development type photosensitive resin composition of the present invention, 1 to 20% by mass, particularly 3 to 12% by mass is preferable.

A solvent can be further added to the radically polymerizable composition of the present invention. The solvent is usually a solvent that can dissolve or disperse each of the above components (polymerization initiator of the present invention and a polymerizable compound having an ethylenically unsaturated bond) as necessary, such as methyl ethyl ketone, methyl amyl ketone. , Diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like ketones; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether Ether solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc .; ethylene glycol monomethyl ether, Cellosolve solvents such as tylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, xylene; hexane Aliphatic hydrocarbon solvents such as benzene, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Minera Paraffinic solvents such as Spirit, Swazol # 310 (Cosmo Matsuyama Petroleum), Solvesso # 100 (Exxon Chemical); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; Examples thereof include methyl pyrrolidone; dimethyl sulfoxide; water and the like, and these solvents can be used as one or a mixture of two or more.
Among these, ketones, ether ester solvents, and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable in the radical polymerizable composition because the compatibility between the resist and the polymerization initiator is good.

  Moreover, the radically polymerizable composition (especially alkali-developable photosensitive resin composition) of the present invention may further contain a coloring material to form a colored alkali-developable photosensitive composition. Examples of the coloring material include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with an epoxy resin, carbon black previously dispersed with a resin in a solvent, 20 to 200 mg / g of resin adsorbed, carbon black treated with an acidic or alkaline surface, average Graphite having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ² of the surface area of carbon black; Graphite , Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series , Ferrocyanide Organic or inorganic such as phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber Pigments can be used. These pigments can be used alone or in combination.

  Commercially available pigments can also be used as the pigment, 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.

  As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

  In the radically polymerizable composition of the present invention, the content of the colorant is preferably 1 to 350 parts by mass, more preferably 10 to 100 parts, relative to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. Part by mass.

The radically polymerizable composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, 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. are mentioned.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the radically polymerizable composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by mass, more preferably 10 parts per 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. It is -800 mass parts. These inorganic compounds can be used alone or in combination of two or more.

  These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  To the radically polymerizable composition of the present invention, a dispersant for dispersing the colorant and / or the inorganic compound can be added. The dispersing agent is not limited as long as it can disperse and stabilize a coloring material or an inorganic compound, and a commercially available dispersing agent such as BYK series manufactured by BYK Chemie Corporation can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof. And those having an amine value of 1 to 100 mgKOH / g are preferably used.

  In the radically polymerizable composition of the present invention, another polymerization initiator can be used in combination with the compound of the present invention. As other polymerization initiators that can be used in combination, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1 -Dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-buty Rubenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl)- s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine , Camphorquinone, N-1414, N-1717, N-1919, NCI-831, NCI-930 (manufactured by ADEKA) IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), benzoyl peroxide, compounds represented by the following general formula (IV), and the like. When these other polymerization initiators are used, The amount used is preferably 1 mass times or less the amount of the compound of the present invention. These polymerization initiators can be used alone or in combination of two or more.

（式中、Ｒ^２１及びＲ^２２は、それぞれ独立に、水素原子、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^２３及びＲ^２４は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ^２５、ＯＲ^２６、ＳＲ^２７、ＮＲ^２８Ｒ^２９、ＣＯＲ^３０、ＳＯＲ^３１、ＳＯ_２Ｒ^３２又はＣＯＮＲ^３３Ｒ^３４を表し、Ｒ^２３及びＲ^２４は、互いに結合して環を形成していてもよく、
Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３及びＲ^３４は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｘ^２は、酸素原子、硫黄原子、セレン原子、ＣＲ^３５Ｒ^３６、ＣＯ、ＮＲ^３７又はＰＲ^３８を表し、
Ｘ^３は、単結合又はＣＯを表し、
Ｒ^３５、Ｒ^３６、Ｒ^３７及びＲ^３８は、それぞれ独立に水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、上記アルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環基で置換されていてもよく、−Ｏ−で中断されていてもよく、
Ｒ^３５、Ｒ^３６、Ｒ^３７及びＲ^３８は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよく、
ａは、０〜４の整数を表し、
ｂは、０〜５の整数を表す。）

(In the formula, R ²¹ and R ²² are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ²³ and R ²⁴ are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ²⁵ , OR ²⁶ , SR ²⁷ , NR ²⁸ R ²⁹ , COR ³⁰ , SOR ³¹ , SO ₂ R ³² or CONR ³³ R ³⁴ , R ²³ and R ²⁴ may be bonded to each other to form a ring;
R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ³⁵ R ³⁶ , CO, NR ³⁷ or PR ³⁸ ,
X ³ represents a single bond or CO,
R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms. And the methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a heterocyclic group, and may be interrupted with -O-. ,
R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

  In addition, the radical polymerizable composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as an antifoaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect promoter, a crosslinking agent, and a thickener can be added. .

  In the radically polymerizable composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond and an optional component other than the compound of the present invention (however, the above-mentioned other polymerization initiator and ethylenically unsaturated group are included. The amount of the alkali-developable compound, inorganic compound (filler), coloring material and solvent excluded) may be appropriately selected according to the purpose of use and is not particularly limited. The total amount is 50 parts by mass or less with respect to 100 parts by mass of the polymerizable compound having a saturated bond.

Moreover, the radically polymerizable composition of the present invention can improve the properties of the cured product by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples thereof include polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin and the like. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. Arbitrariness.
When using another organic polymer, the usage-amount is preferably 10-500 mass parts with respect to 100 mass parts of polymeric compounds which have the said ethylenically unsaturated bond.

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

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

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

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

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Examples include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  The radical polymerizable composition of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, It can be applied on a supporting substrate such as plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The light source of the energy beam used for curing the radical polymerizable composition of the present invention includes an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp. , Carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc. High energy rays can be used, and preferably, an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc., that emit light having a wavelength of 300 to 450 nm are used.

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

  The radical polymerizable composition of the present invention comprises a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a portable information terminal, a digital camera; Color filter of CCD image sensor; Electrode material for plasma display panel; Powder coating; Printing plate; Adhesive; Dental composition; Gel coat; Photoresist for electronics; Electroplating resist; Etch resist; Resist for manufacturing color filters for display applications or for forming structures in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs; compositions for encapsulating electrical and electronic components; magnetic recording materials Micromachine parts; waveguides; optical switches; plating masks; Color test system; Glass fiber cable coating; Screen printing stencil; Material for producing three-dimensional objects by stereolithography; Holographic recording material; Image recording material; Microelectronic circuit; Decoloring material; Image recording material Decolorizing material for image recording materials using microcapsules; photoresist material for printed wiring boards; photoresist material for UV and visible laser direct imaging systems; dielectric layer formation in sequential lamination of printed circuit boards It can be used for various applications such as a photoresist material or a protective film used in the invention, and the application is not particularly limited.

  The radically polymerizable composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertical alignment type liquid crystal display element. In particular, it is useful as a radical polymerizable composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.

  The spacer for a liquid crystal display panel includes (1) a step of forming a coating film of the radical polymerizable composition of the present invention on a substrate, and (2) radiation through a mask having a predetermined pattern shape on the coating film. Preferably, it is formed by an irradiation step, (3) a baking step after exposure, (4) a step of developing the coating after exposure, and (5) a step of heating the coating after development.

  The (colored) radically polymerizable composition of the present invention to which an ink repellent agent is added is useful as a partition-forming resin composition for an inkjet system, and the composition is used for a color filter, and particularly has a profile angle of 50 ° or more. It is preferably used for an inkjet color filter partition wall. As the ink repellent agent, a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.

  An optical element by a method in which a partition formed from the radically polymerizable composition of the present invention partitions an image-receiving body, and droplets are applied to the recessed portions on the partitioned image-receiving body by an ink jet method to form an image area. Is manufactured. At this time, it is preferable that the droplet contains a colorant and the image region is colored, and a pixel group composed of a plurality of colored regions and at least a partition wall separating the colored regions of the pixel group on the substrate. And an optical element produced by the above-described optical element manufacturing method is preferably used.

  The radically polymerizable composition of the present invention is also used as a composition for a protective film or an insulating film, and contains an ultraviolet absorber, an alkylated modified melamine and / or an acrylic modified melamine, 1 or 2 containing an alcoholic hydroxyl group in the molecule. Functional (meth) acrylate monomers and / or silica sols can be included.

As a radical polymerizable composition for the protective film and insulating film,
(A) a carboxyl group-containing resin obtained by reacting a diol compound and a polyvalent carboxylic acid, having a weight average molecular weight of 2,000 to 40,000 and an acid value of 50 to 200 mgKOH / g,
(B) an unsaturated compound containing at least one polymerizable ethylenically unsaturated bond in one molecule,
(C) an epoxy compound, and (D) a polymerization initiator represented by the above general formula (I),
A resin composition mainly composed of
The total amount of (A) component and (B) component is 100 parts by weight, and (C) component is contained in 10 to 40 parts by weight, (D) component is contained in 0.01 to 2.0 parts by weight, and (D It is preferable that the compound contains a compound represented by the general formula (I) as a polymerization initiator.

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

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

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Examples 1 and 2] Compound No. 1 5 and compound no. 9 production

1.2 eq. Of carboxylic acid derivative 1 And 1.0 eq. Was dissolved in tetrahydrofuran (twice the theoretical yield), N, N-diisopropylcarbodiimide was added under ice cooling, and the mixture was stirred at room temperature for 24 hours. The insoluble material was filtered off and purified by chromatography on a silica gel column (n-hexane: ethyl acetate = 1: 1), dried and dried. 5 and no. 9 were obtained respectively.
In Example 1, as the carboxylic acid derivative 1, in the carboxylic acid derivative 1 in [Chemical Formula 10], R ¹ and R ² form a morpholine ring, and R ³ , R ⁴ , R ⁹ and R ¹⁰ is a methyl group, R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, and n is divalent. Further, in the alcohol derivative 1 in [Chemical Formula 10], Y is the above formula (I-1), R ^{1 ′} and R ^{2 ′} form a morpholine ring, and R ^{3 ′} and R ⁴ Is a methyl group, R ^{5 ′} , R ^{6 ′} , R ^{7 ′} and R ^{8 ′} are hydrogen, and X is —CH ₂ CH ₂ S—.
Further, in Example 2, as the carboxylic acid derivative 1, in the carboxylic acid derivative 1 in [Chemical Formula 10], R ¹ and R ² form a morpholine ring, and R ³ , R ⁴ , R ⁹ and R ¹⁰ is a methyl group, R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, and n is 2. In addition, in the alcohol derivative 1 in [Chemical Formula 5], Y is the formula (I-2), R ¹² and R ¹³ are methyl groups, X ² is CO, and X ³ is sulfur. An atom in which R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are hydrogen and X is —CH ₂ CH ₂ O— was used.
The obtained Compound No. 5 and no. The analysis results for 9 minutes are shown in [Table 1] to [Table 3].

[Examples 1 and 2] Alkali-developable photosensitive resin composition No. 1 1 and no. 2 SPC-1000 (acrylic resin; manufactured by Showa Denko) 54.84 g, Aronix M-450 (polyfunctional acrylate; manufactured by Toa Gosei Co., Ltd.) 12.77 g, KBE-403 (silane coupling agent; manufactured by Shin-Etsu Silicone) 0.57 g, 3.19 g of a 1% cyclohexanone solution of FZ-2122 (surfactant; manufactured by Nihon Unicar) and 27.95 g of propylene glycol-1-monomethyl ether-2-acetate were mixed, and then 14. 805 g was weighed and the compound No. obtained in Examples 1 and 2 was used. 5 and no. No. 9 of 0.195 g was added and stirred well, and the alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. 1 and no. 2 was obtained.

[Comparative Example 1] Comparative alkali-developable photosensitive resin composition No. Preparation of Compound No. 1 obtained in Example 1 Comparative alkali-developable photosensitive resin composition No. 5 was prepared in the same manner as in Example 1 except that 5 was replaced with 2-morpholyl-2- (4′-methylmercapto) benzoylpropane. 1 was obtained.

[Evaluation Examples 1-1 and 1-2 and Comparative Evaluation Example 1] Sublimation evaluation compound No. 1 5 and no. 9 and the comparative compound (2-morpholyl-2- (4′-methylmercapto) benzoylpropane) were evaluated for sublimation as follows.
That is, Compound No. 5 and no. 9 and 2.5 mg of the comparative compound were each held at 150 ° C. for 1 hour in a nitrogen atmosphere, and the weight reduction ratio was calculated to evaluate sublimation. The test results are shown in [Table 4].

From the above [Table 4], compound No. 1 which is a compound represented by the above general formula (I). 5 and no. No. 9 is clearly low in sublimability.

[Evaluation Examples 2-1 and 2-2 and Comparative Evaluation Example 2] Evaluation of Radiation Sensitivity The obtained alkali-developable photosensitive resin composition No. 1 and no. 2 and comparative alkali-developable photosensitive resin composition No. 2 1 was evaluated as follows.
That is, the alkali-developable photosensitive resin composition was spin coated on a glass substrate, prebaked at 90 ° C. for 90 seconds using a hot plate, and exposed through a mask using a high-pressure mercury lamp as a light source. After developing using a 2.5% by mass aqueous sodium carbonate solution as a developing solution, it was washed thoroughly with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. The height of the pattern was measured using a stylus type surface shape measuring instrument (manufactured by Keyence), and the residual film ratio (%) was obtained from the following formula to determine the radiation sensitivity. The exposure dose giving a residual film ratio of 70% or more is evaluated as A when the ~200mJ / cm ^2, was evaluated as B when 200~500mJ / cm ^2, when the 500 mJ / cm ² is a C evaluated. The test results are shown in [Table 5].
Residual film ratio (%) = (pattern height after post-baking / initial film thickness) × 100

  From the above [Table 5], it is clear that the compound represented by the general formula (I) is equivalent to the comparative compound and excellent in radiation sensitivity.

Therefore, the compound represented by the general formula (I) is useful as a polymerization initiator because it has low sublimation while maintaining sensitivity.

Claims (4)

The compound represented by the following general formula (I).

(Wherein R ¹ and R ² are each independently a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or an unsubstituted alkyl group having 1 to 12 carbon atoms; An alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, halogen atoms, an arylalkyl group or unsubstituted having 7 to 30 carbon atoms which is substituted with a cyano group or a nitro group; an alkenyl group having 2 to 12 carbon atoms, R ¹ and R ^2, connected respectively May form a 3- to 6-membered heterocyclic ring,
R ³ and R ⁴ are each independently a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted alkyl group having 1 to 12 carbon atoms; An alkyl group having 4 to 4 alkyl groups, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and 1 to 4 carbon atoms An alkoxy group, an amino group, an alkylthio group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms; 2 to 12 alkenyl groups; R ³ and R ⁴ may be linked to form a 3- to 6-membered cyclic alkane;
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group; an alkyl having 1 to 8 carbon atoms that is substituted or unsubstituted by a halogen atom A group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and when n is 2 or more, they are the same or different,
n represents a number from 1 to 12,
X is a divalent organic group,
Y is a structure represented by the following formula (I-1) or (I-2),
The methylene chain in the above alkyl group and arylalkyl group and alkylene group is replaced with —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O—. It may be done. )

Wherein R ^{1 ′} and R ^{2 ′} are each independently a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or an unsubstituted alkyl group having 1 to 12 carbon atoms. Group: an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group A group, a halogen atom, a cyano group or a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms; an alkenyl group having 2 to 12 carbon atoms, wherein R ^{1 ′} and R ^{2 ′} are , Each may be linked to form a 3- to 6-membered heterocyclic ring,
R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom; a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted alkyl group having 1 to 12 carbon atoms; a carbon atom An alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted phenyl group; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and 1 to 1 carbon atoms 4 alkoxy groups, amino groups, alkylthio groups having 1 to 4 carbon atoms, carboxyl groups, halogen atoms, cyano groups, nitro groups, or unsubstituted arylalkyl groups having 7 to 30 carbon atoms; carbon Represents an alkenyl group having 2 to 12 atoms, R ^{3 ′} and R ^{4 ′} may be linked to form a 3- to 6-membered cyclic alkane;
R ^{5 ′} , R ^{6 ′} , R ^{7 ′,} and R ^{8 ′} each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group; a halogen atom-substituted or unsubstituted carbon atom of 1 An alkyl group having ˜8; an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or an unsubstituted arylalkyl group having 7 to 30 carbon atoms ,
The methylene chain in the above alkyl group and arylalkyl group and alkylene group is replaced with —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O—. It may be done. )

Wherein R ¹² and R ¹³ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ²² , OR ²³ , SR ²⁴ , NR ²⁵ R ²⁶ , COR ²⁷ , SOR ²⁸ , SO ₂ R ²⁹ or CONR ³⁰ R ³¹ , R ¹⁶ and R ¹⁸ may be bonded to each other to form a ring,
R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents a single bond or CO,
X ³ represents an oxygen atom, a sulfur atom, a selenium atom, CR ³² R ³³ , CO, NR ³⁴ or PR ³⁵ ,
R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. Represents a heterocyclic group of formula 2 to 20,
Carbons in R ¹² , R ¹³ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ The methylene group in the alkyl group having 1 to 20 atoms or the arylalkyl group having 7 to 30 carbon atoms may be substituted with a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group or heterocyclic group, The methylene chain in the alkyl group or arylalkyl group may be interrupted by -O-. )   A polymerization initiator containing the compound according to claim 1.   A radically polymerizable composition obtained by adding a polymerizable compound having an ethylenically unsaturated bond to the polymerization initiator according to claim 2. Hardened | cured material formed by irradiating an energy ray to the radically polymerizable composition of Claim 3.