JP2016196437A - Oxime ester compound and photopolymerization initiator comprising the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxime ester compound that has excellent stability, has low sublimability, has excellent developability, has high transmittance in a visible light region, has high solubility in organic solvent, efficiently generates radicals for a bright line of 365 nm (i line) and the like, and is useful as a photopolymerization initiator for a photosensitive composition.SOLUTION: The present invention relates to a specific oxime ester compound having a carbazole skeleton, or an oxime ester compound having a diphenyl sulfide skeleton represented by formula (II) (Y is S; R-Rare H, a C1-20 alkyl group or the like; Ris OH, COOH, HOCHCHO- or the like).SELECTED DRAWING: None

Description

  The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator for use in a photosensitive composition, a photopolymerization initiator containing the compound, and a polymerizability having an ethylenically unsaturated bond in the photopolymerization initiator. The present invention relates to a photosensitive composition containing a compound.

  The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating energy rays (light). It is used for photosensitive printing plates and various photoresists.

As photopolymerization initiators used in the photosensitive composition, Patent Documents 1 to 3 below propose using oxime ester compounds.
However, among the oxime ester compounds described in the above-mentioned patent documents, oxime ester compounds having satisfactory sensitivity have a problem of low transmittance in the visible light region and a desired color cannot be obtained with a color filter (particularly, the protective film). In the case of such a transparent photosensitive composition or a resist for a color filter using a blue pigment or dye, a compound having an absorption at 380 to 450 nm is mixed, and the lightness and color purity are reduced). The oxime ester compound having a high transmittance has a problem that the sensitivity is not sufficiently satisfactory, and a photopolymerization initiator having both characteristics has been demanded.

  Further, a colored alkali-developable photosensitive resin composition containing a color material such as a color filter is required to have high sensitivity and high solubility in an organic solvent, and a high concentration of a photopolymerization initiator in the resist. It is necessary to make it. However, a high concentration photopolymerization initiator has caused residues due to deterioration of developability, contamination of the photomask and heating furnace due to sublimation, and the like.

JP 2000-80068 specification Special table 2006-516246 specification International Publication 2013/008652

  The problem to be solved is that there has been no photopolymerization initiator that has satisfactory sensitivity, high solubility in organic solvents, low outgas generation, and high visible light transmittance. is there.

  Accordingly, the object of the present invention is to provide excellent stability, low outgas generation, low sublimation, excellent developability, high visible light transmittance, high solubility in organic solvents, and 365 nm. It is an object of the present invention to provide a novel compound useful as a highly sensitive photopolymerization initiator that efficiently absorbs and activates near-ultraviolet light, a photopolymerization initiator using the compound, and a photosensitive composition.

  The present invention achieves the above object by providing a novel oxime ester compound represented by the following general formula (I) or (II) and a photopolymerization initiator containing the compound.

（式中、Ｒ¹及びＲ²はそれぞれ独立に、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、Ｒ¹¹、Ｒ¹²及びＲ¹³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、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、Ｒ¹¹、Ｒ¹²及びＲ¹³で表わされる置換基の水素原子は、ＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＮＲ²²Ｒ²³、ＣＯＮＲ²²Ｒ²³、−ＮＲ²²−ＯＲ²³、−ＮＣＯＲ²²−ＯＣＯＲ²³、−Ｃ（＝Ｎ−ＯＲ²¹）−Ｒ²²、−Ｃ（＝Ｎ−ＯＣＯＲ²¹）−Ｒ²²、ＣＮ、ハロゲン原子、又はＣＯＯＲ²¹で置換される場合もあり、
Ｒ²¹、Ｒ²²及びＲ²³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、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、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基の水素原子は、ＣＮ、ハロゲン原子、水酸基又はカルボキシル基で置換される場合もあり、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基のアルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ²⁴−、−ＮＲ²⁴ＣＯＯ−、−ＯＣＯＮＲ²⁴−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断される場合もあり、Ｒ²⁴は、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、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、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基のアルキル部分は、分岐側鎖がある場合や環状アルキルである場合があり、また、Ｒ¹²とＲ¹³及びＲ²²とＲ²³はそれぞれ一緒になって環を形成する場合もあり、Ｒ³は、Ｒ¹¹、ＯＲ¹¹、ＳＲ¹¹、ＣＯＲ¹⁴、ＣＯＮＲ¹⁵Ｒ¹⁶、ＮＲ¹²ＣＯＲ¹¹、ＯＣＯＲ¹¹、ＣＯＯＲ¹⁴、ＳＣＯＲ¹¹、ＯＣＳＲ¹¹、ＣＯＳＲ¹⁴、ＣＳＯＲ¹¹、水酸基、ニトロ基、ＣＮ又はハロゲン原子を表し、
Ｌ¹、Ｌ²及びＬ³は水素原子、Ｒ¹¹、ＯＲ¹¹、ＳＲ¹¹、ＣＯＲ¹⁴、ＣＯＮＲ¹⁵Ｒ¹⁶、ＮＲ¹²ＣＯＲ¹¹、ＯＣＯＲ¹¹、ＣＯＯＲ¹⁴、ＳＣＯＲ¹¹、ＯＣＳＲ¹¹、ＣＯＳＲ¹⁴、ＣＳＯＲ¹¹、水酸基、ニトロ基、ＣＮ又はハロゲン原子を表し、Ｌ¹とＲ³、Ｒ³とＬ²及びＬ²とＬ³はそれぞれ一緒になって環を形成する場合もあり、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、水素原子又は炭素原子数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、Ｒ⁴は、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、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、Ｒ⁴で表される基のアルキル部分は、分岐側鎖がある場合や環状アルキルである場合があり、Ｒ⁴で表わされる基の水素原子は、更にＲ²¹、ＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＮＲ²²Ｒ²³、ＣＯＮＲ²²Ｒ²³、−ＮＲ²²−ＯＲ²³、−ＮＣＯＲ²²−ＯＣＯＲ²³、ＮＲ²²ＣＯＲ²¹、ＯＣＯＲ²¹、ＣＯＯＲ²¹、−Ｃ（＝Ｎ−ＯＲ²¹）−Ｒ²²、−Ｃ（＝Ｎ−ＯＣＯＲ²¹）−Ｒ²²、ＳＣＯＲ²¹、ＯＣＳＲ²¹、ＣＯＳＲ²¹、ＣＳＯＲ²¹、水酸基、ニトロ基、ＣＮ、ハロゲン原子、又はＣＯＯＲ²¹で置換される場合もあり、Ｘは、直接結合、ＣＯまたは下記一般式（Ｉ−Ａ）で表される基を表す。）

(Wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN; R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; Represents an atom, 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 heterocyclic group having 2 to 20 carbon atoms, R ¹¹ , R The hydrogen atom of the substituent represented by ¹² and R ¹³ is OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR ²² —OCOR ²³ , —C ( ═N—OR ²¹ ) —R ²² , —C (═N—OCOR ²¹ ) —R ²² , CN, halogen atom, or COOR ²¹ ,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, 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. The hydrogen atom of the substituent represented by the number 2-20 heterocyclic group represented by R ²¹ , R ²² and R ²³ may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,
The alkylene part of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, — NR ²⁴ COO—, —OCONR ²⁴ —, —SCO—, —COS—, —OCS—, or —CSO— may be interrupted 1 to 5 times, and R ²⁴ is a hydrogen atom or a carbon atom number of 1 to 20 An alkyl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R ¹¹ , R ¹² , R ¹³ , R ²¹ , The alkyl part of the substituent represented by R ²² and R ²³ may have a branched side chain or may be a cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ are combined together. In some cases, a ring is formed, and R ³ is R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , a hydroxyl group, a nitro group, CN or a halogen atom,
L ¹ , L ² and L ³ are hydrogen atoms, R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ^{11 represents} a hydroxyl group, a nitro group, CN or a halogen atom, and L ¹ and R ³ , R ³ and L ^2, and L ² and L ³ may form a ring together, and R ¹⁴ , R ¹⁵ And R ¹⁶ represents a hydrogen atom or 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 heterocyclic group having 2 to 20 carbon atoms. R ⁴ represents a hydrogen atom, 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 heterocyclic group having 2 to 20 carbon atoms. the stands, alkyl moiety of the group represented by R ⁴ is May be the case or cyclic alkyl with branched side chains, hydrogen atom of the groups represented by R ⁴ may further ^{R 21, OR 21, COR 21} , SR 21, NR 22 R 23, CONR 22 R 23, - ^{NR 22 -OR 23, -NCOR 22 -OCOR} 23, NR 22 COR 21, OCOR 21, COOR 21, -C (= N-OR 21) -R 22, -C (= N-OCOR 21) -R 22, SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN, halogen atom, or COOR ²¹ may be substituted, and X is a direct bond, CO, or the following general formula (IA) Represents the group represented. )

（式中、Ｚ¹及びＺ²は、結合手であって、単結合、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、
Ｚ¹及びＺ²で表される結合手のアルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ²⁴−、−ＮＲ²⁴ＣＯＯ−、−ＯＣＯＮＲ²⁴−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断される場合もあり、Ｚ²で表される結合手のアルキレン部分は分岐側鎖がある場合や環状アルキレンである場合もある。
Ｒ⁵は、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、Ｒ¹¹、Ｒ¹²及びＲ¹³は、上記一般式（Ｉ）と同じである。）

(In the formula, Z ¹ and Z ² are a bond, a single bond, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms. Or a heterocyclic group having 2 to 20 carbon atoms,
The alkylene part of the bond represented by Z ¹ and Z ² is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ COO—, —OCONR ²⁴ —, —SCO. It may be interrupted 1 to 5 times by —, —COS—, —OCS— or —CSO—, and the alkylene part of the bond represented by Z ² may be a branched side chain or a cyclic alkylene. is there.
R ⁵ represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (I). )

（式中、Ｒ⁶、Ｒ⁷及びＲ⁸はそれぞれ独立に、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、Ｒ¹¹、Ｒ¹²及びＲ¹³は、上記一般式（Ｉ）と同じであり、
Ｒ⁹は、ＯＨ、ＣＯＯＨ又は下記一般式（ＩＩ−Ａ）で表される基を表し、
Ｙは、酸素原子、硫黄原子、セレン原子、ＣＲ³¹Ｒ³²、ＣＯ、ＮＲ³³又はＰＲ³⁴を表し、αは１〜１０の整数を表し、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴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、
Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴で表される置換基のアルキル部分は、分岐側鎖がある場合や環状アルキレンである場合もあり、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴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する場合もある。）

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ represent the above general formulas) Same as formula (I),
R ⁹ represents OH, COOH or a group represented by the following general formula (II-A),
Y represents an oxygen atom, a sulfur atom, a selenium atom, CR ³¹ R ³² , CO, NR ³³ or PR ³⁴ , α represents an integer of 1 to 10, and R ³¹ , R ³² , R ³³ and R ³⁴ represent Each independently represents 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;
The alkyl part of the substituent represented by R ³¹ , R ³² , R ³³ and R ³⁴ may have a branched side chain or a cyclic alkylene, and R ³¹ , R ³² , R ³³ and R ³⁴ may be Each may independently form a ring together with one of the adjacent benzene rings. )

（式中、Ｚ³は、結合手であって、−Ｏ−、−Ｓ−、−ＮＲ²²−、−ＮＲ²²ＣＯ−、−ＳＯ₂−、−ＣＳ−、−ＯＣＯ−又は−ＣＯＯ−を表し、
Ｚ⁴は、結合手であって、１〜３のＲ¹⁰で置換される炭素原子数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、
Ｚ⁴で表される結合手のアルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ²⁴−、−ＮＲ²⁴ＣＯＯ−、−ＯＣＯＮＲ²⁴−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断される場合もあり、Ｚ⁴で表される結合手のアルキレン部分は分岐側鎖がある場合や環状アルキレンである場合もあり、Ｒ¹⁰は、ＯＲ⁴¹、ＳＲ⁴¹、ＣＯＮＲ⁴²Ｒ⁴³、ＮＲ⁴²ＣＯＲ⁴³、ＯＣＯＲ⁴¹、ＣＯＯＲ⁴¹、ＳＣＯＲ⁴¹、ＯＣＳＲ⁴¹、ＣＯＳＲ⁴¹、ＣＳＯＲ⁴¹、ＣＮ又はハロゲン原子を表し、Ｒ⁴¹、Ｒ⁴²及びＲ⁴³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、Ｒ⁴¹、Ｒ⁴²及びＲ⁴³で表される置換基のアルキル部分は分岐側鎖がある場合や環状アルキレンである場合もあり、Ｒ⁴²とＲ⁴³は、一緒になって環を形成する場合もあり、ａは１〜３の整数を表す。Ｒ²²及びＲ²⁴は、上記一般式（Ｉ）と同じである。）

(In the formula, Z ³ is a bond, and represents —O—, —S—, —NR ²² —, —NR ²² CO—, —SO ₂ —, —CS—, —OCO— or —COO—. Represent,
Z ⁴ is a bond and is 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, which is substituted with 1 to 3 R ^10. Or a heterocyclic group having 2 to 20 carbon atoms,
The alkylene part of the bond represented by Z ⁴ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ COO—, —OCONR ²⁴ —, —SCO—, — It may be interrupted 1 to 5 times by COS-, -OCS- or -CSO-, and the alkylene part of the bond represented by Z ⁴ may have a branched side chain or a cyclic alkylene, and R ¹⁰ represents OR ⁴¹ , SR ⁴¹ , CONR ⁴² R ⁴³ , NR ⁴² COR ⁴³ , OCOR ⁴¹ , COOR ⁴¹ , SCOR ⁴¹ , OCSR ⁴¹ , COSR ⁴¹ , CSOR ⁴¹ , CN or a halogen atom, R ⁴¹ , R ⁴² and R ⁴³ independently represents 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 R ⁴¹ , R ⁴² and a substituent represented by R ⁴³ Kill moiety sometimes is the case or cyclic alkylene there is branched side chain, R ⁴² and R ⁴³ are sometimes taken together to form a ring, a is an integer of 1-3. R ²² and R ²⁴ are the same as those in the general formula (I). )

Moreover, this invention provides the photosensitive composition formed by making the said photoinitiator contain the polymeric compound which has an ethylenically unsaturated bond.
Moreover, this invention provides the alkali developable photosensitive resin composition formed by making the said photosensitive composition contain the polymeric compound which has group which gives alkali developability.
The present invention also provides a colored alkali-developable photosensitive resin composition obtained by further adding a coloring material to the alkali-developable photosensitive resin composition.

  Moreover, this invention provides the hardened | cured material formed by irradiating the said photosensitive composition, alkali developable photosensitive resin composition, or colored alkali developable photosensitive resin composition with an energy beam.

  The oxime ester compound of the present invention has excellent stability, low sublimation, excellent developability, high transmittance in the visible light region, high solubility in organic solvents, and bright lines such as 365 nm (i-line). Is useful as a photopolymerization initiator used in a photosensitive composition.

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

The oxime ester compound of the present invention is a novel compound represented by the above general formula (I) or (II). The oxime ester compound has geometric isomers due to oxime double bonds, but these are not distinguished.
That is, in this specification, the compound represented by the above general formula (I) or (II), and the following general formula (III), general formula (IV), and general formula (V), which are preferred forms of the compound described later, are described below. And the compound represented by the general formula (VI) and the exemplified compound thereof represent a mixture of both or one of them, and are not limited to the structure showing the isomer.

In the general formula (I), R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 and the} general formula (II) R ¹¹ , R ¹² , R ¹³ , R ²² , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² and R ⁴³ as an alkyl group having 1 to 20 carbon atoms Is, for example, 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, cycl Hexyl ethyl, and the like.

In the general formula (I), R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 and the} general formula (II) R ¹¹ , R ¹² , R ¹³ , R ²² , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² and R ⁴³ as an aryl group having 6 to 30 carbon atoms Examples thereof include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, and phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups.

In the general formula (I), R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 and the} general formula (II) R ¹¹ , R ¹² , R ¹³ , R ²² , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² and R ⁴³ and an arylalkyl group having 7 to 30 carbon atoms Examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

In the general formula (I), R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 and the} general formula (II) , R ¹¹ , R ¹² , R ¹³ , R ²² , R ²⁴ , as the heterocyclic group having 2 to 20 carbon atoms, for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole Preferred examples include 5- to 7-membered heterocycles such as 2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl and the like.

In the general formula (I), R ¹² and R ¹³ , R ²² and R ²³ , and in the general formula (II), R ⁴² and R ⁴³ may be formed together, and R ³¹ , R Examples of the ring that R ³² , R ³³ and R ³⁴ can form together with the adjacent benzene ring include, for example, a cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. Preferred examples thereof include 5- to 7-membered rings.

In the general formula (II), Z ⁴ is a bond, and is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon atoms substituted with 1 to 3 R ^10. An arylalkyl group having 7 to 30 atoms or a heterocyclic group having 2 to 20 carbon atoms is represented.

Examples of the alkyl group having 1 to 20 carbon atoms that is substituted with 1 to 3 R ¹⁰ include, for example, when a is 1, methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methyl. Propylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, Examples include pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tridecylene, tetradecylene, pentadecylene, ethane-1,1-diyl, propane-2,2-di1yl and the like.

Examples of the aryl group having 6 to 30 carbon atoms substituted by 1 to 3 R ¹⁰ include, for example, when a is 1, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2 , 6-naphthylene, 1,4-naphthylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,4′-diyl, 2,2-diphenylpropane-4,4′-diyl, diphenyl sulfide-4 , 4′-diyl, diphenylsulfone-4,4′-diyl, and the like.

Examples of the arylalkyl group having 7 to 30 carbon atoms substituted by 1 to 3 R ¹⁰ include, for example, when a is 1, an arylalkylene group such as a linking group represented by [Chemical Formula 5]. It is done.

（式中、＊は結合手を表す。また「Ｃ_n1〜_n2」との記載は、炭素原子数n1〜n2の直鎖状アルキレン基を表す）

(In the formula, * represents a bond, and the description “C _n1 to _n2 ” represents a linear alkylene group having _n1 to _n2 carbon atoms)

The heterocyclic group having 2 to 20 carbon atoms which is substituted with R ¹⁰ 1-3, for example, when a is 1, 2,5-pyridinediyl, 2,6-pyridinediyl, 2, 5-pyrimidinediyl, 2,5-thiophenediyl, 3,4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazoldiyl, 2,5-benzofurandiyl, 2,5 -A divalent heterocyclic group such as benzothiophenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazolediyl, 2,5-benzoxazolediyl, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms, which is a bond represented by Z ¹ , Z ² and Z ⁵ , are represented by Z ⁴ and have 1 to 1 carbon atoms substituted with a R ¹⁰ . Examples of the case in which a of the 20 alkyl groups is 1 include the same groups as mentioned above. Similarly, examples of the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms and the heterocyclic group having 2 to 20 carbon atoms represented by Z ¹ , Z ¹ and Z ⁵ include , Each of a is an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms and a heterocyclic group having 2 to 20 carbon atoms, which is represented by Z ⁴ and substituted with a R ^10. Examples of 1 include the same groups as those mentioned above.

In addition, in the general formula (II), a halogen atom represented by R ¹⁰ , a halogen atom represented by R ³ , L ¹ , L ² and L ³ in the general formula (I), R ⁴ , Examples of the halogen atom that may substitute R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include fluorine, chlorine, bromine and iodine.

In the general formula (I) or (II), the substituents represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ , and the general formula (I) or (II) , Z ¹ , Z ² , Z ⁴ and Z ⁵ are represented by —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ CO—, It may be interrupted 1 to 5 times by —NR ²⁴ COO—, —OCONR ²⁴ —, —SCO—, —COS—, —OCS—, or —CSO—. In some cases, the above-mentioned groups may be interrupted, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted in succession.
In the general formula (I) or (II), the substituents represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ , and the general formula (I) or (II) Among them, substituents represented by R ³¹ , R ³² , R ³³ and R ³⁴ , bonds represented by Z ² , Z ⁴ and Z ⁵ , and substitutions represented by R ⁴¹ , R ⁴² and R ⁴³ The alkyl (alkylene) portion of the group may be a branched side chain or a cyclic alkyl (cyclic alkylene).

  Among the oxime ester compounds of the present invention, the compound represented by any one of the following general formula (III), general formula (IV), general formula (V) and general formula (VI) is excellent in stability and low sublimation. , Excellent developability, high transmittance in the visible light region, high solubility in organic solvents, high effect of efficiently generating radicals for emission lines such as 365 nm (i-line), and further manufacturing Is preferable because it is easy.

（式中、Ｚ⁵は、結合手であって、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、Ｚ⁵で表される結合手のアルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ²⁴−、−ＮＲ²⁴ＣＯＯ−、−ＯＣＯＮＲ²⁴−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断される場合もあり、Ｚ⁵で表される結合手のアルキレン部分は分岐側鎖がある場合や環状アルキレンである場合もある。Ｒ¹、Ｒ²、Ｒ²¹、Ｒ²²、Ｒ²⁴、Ｌ¹、Ｌ²及びＬ³は、一般式（Ｉ）と同義である。）

(In the formula, Z ⁵ is a bond and is 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 2 to 2 carbon atoms. The alkylene part of the bond represented by 20 heterocyclic groups and represented by Z ⁵ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ COO—, —OCONR. ^24- , -SCO-, -COS-, -OCS- or -CSO- may be interrupted 1 to 5 times, and the alkylene part of the bond represented by Z ⁵ may be cyclic or cyclic. (It may be alkylene. R ¹ , R ² , R ²¹ , R ²² , R ²⁴ , L ¹ , L ² and L ³ have the same meanings as those in formula (I).)

（式中、環Ａは炭素原子数１〜２０の五員環または六員環の炭化水素環を表し、環Ａ中の水素原子は、更にＲ²¹、ＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＮＲ²²Ｒ²³、ＣＯＮＲ²²Ｒ²³、−ＮＲ²²−ＯＲ²³、−ＮＣＯＲ²²−ＯＣＯＲ²³、−Ｃ（＝Ｎ−ＯＲ²¹）−Ｒ²²、−Ｃ（＝Ｎ−ＯＣＯＲ²¹）−Ｒ²²、ＣＮ、ハロゲン原子、又はＣＯＯＲ²¹で置換される場合もある。式中にＲ²¹が複数ある場合、Ｒ²¹は同じ場合もあり、異なる場合もある。Ｒ²、Ｒ³、Ｒ²¹、Ｒ²²、Ｒ²³、Ｌ¹、Ｌ²、Ｌ³及びＺ⁵は、一般式（ＩＩＩ）と同義である。βは１〜１０の整数を表す。）

(In the formula, ring A represents a 5- or 6-membered hydrocarbon ring having 1 to 20 carbon atoms, and the hydrogen atom in ring A is further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ^{22 R 23, CONR 22 R 23} , -NR 22 -OR 23, -NCOR 22 -OCOR 23, -C (= N-OR 21) -R 22, -C (= N-OCOR 21) -R 22, CN , halogen atom, or if R ²¹ is s during a. formula which when substituted by COOR ^21, R ²¹ is also the same case, even if different there ^{.R 2, R 3, R 21} , R 22, R ²³ , L ¹ , L ² , L ³ and Z ⁵ have the same meaning as in formula (III), and β represents an integer of 1 to 10.)

（式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｌ¹、Ｌ²及びＬ³は、一般式（Ｉ）と同義である。）

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , L ¹ , L ² and L ³ have the same meanings as in the general formula (I).)

（式中、Ｒ⁶、Ｒ⁷、Ｒ⁸およびＲ⁹は、一般式（ＩＩ）と同義である。）

(In the formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ have the same meaning as in formula (II).)

Examples of the 5-membered ring in the hydrocarbon having 1 to 20 carbon atoms represented by ring A in general formula (IV) include a cyclopentyl ring, a methylcyclopentyl ring, and an ethylcyclopentyl ring. Examples of the 6-membered ring include a cyclohexyl ring, a methylcyclohexyl ring, an ethylcyclohexyl ring, a phenyl group, a benzyl group, and a tolyl group. Hydrogen atoms in the ring A further ^{R 21, OR 21, COR 21} , SR 21, NR 22 R 23, CONR 22 R 23, -NR 22 -OR 23, -NCOR 22 -OCOR 23, -C (= N —OR ²¹ ) —R ²² , —C (═N—OCOR ²¹ ) —R ²² , CN, a halogen atom, or COOR ²¹ , including the number of carbon atoms in these substituents, The number of carbon atoms is “1-20”.

Among the oxime ester compounds of the present invention, R ¹ , R ² , R ²¹ and R ^{22 in the} general formula (III) are alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 30 carbon atoms. The case is preferred because of good developability, and particularly preferred is a methyl group, ethyl group or phenyl group. Further, when Z ⁵ in the general formula (III) is methylene, ethylene or phenylene, it is preferable because synthesis is easy.

Among the oxime ester compounds of the present invention, when R ² in the general formula (IV) is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, the developability is good. Among them, a methyl group, an ethyl group or a phenyl group is particularly preferable. Further, when Z ⁵ in the general formula (IV) is methylene, ethylene or phenylene, it is preferable because synthesis is easy.

Among the oxime ester compounds of the present invention, when R ² in the general formula (V) is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, the developability is good. Among them, a methyl group, an ethyl group or a phenyl group is particularly preferable.
Further, when Z ⁵ in the general formula (V) is methylene, ethylene or phenylene, it is preferable because synthesis is easy.

Among the oxime ester compounds of the present invention, development is performed when R ⁶ , R ⁷ and R ^{8 in the} general formula (VI) are an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms. From the viewpoint of good properties, the methyl group, the ethyl group or the phenyl group is particularly preferable.

  Preferable specific examples of the oxime ester compound of the present invention represented by the general formula (III) include the following compound Nos. 1-No. 10 is mentioned. However, the present invention is not limited by the following compounds. In the chemical formula below, “Me” represents a methyl group, and “Ph” represents a phenyl group.

  Preferable specific examples of the oxime ester compound of the present invention represented by the general formula (IV) include the following compound Nos. 11-No. 30. However, the present invention is not limited by the following compounds. In the chemical formula below, “Me” represents a methyl group, and “Ph” represents a phenyl group.

  Preferable specific examples of the oxime ester compound of the present invention represented by the general formula (V) include the following compound Nos. 31-No. 45. However, the present invention is not limited by the following compounds. In the chemical formula below, “Me” represents a methyl group, and “Ph” represents a phenyl group.

  Preferable specific examples of the oxime ester compound of the present invention represented by the above general formula (VI) include the following compound Nos. 46-No. 57. However, the present invention is not limited by the following compounds. In the chemical formula below, “Me” represents a methyl group, and “Ph” represents a phenyl group.

The method for producing the oxime ester compound of the present invention represented by the above general formula (III) is not particularly limited. For example, it is produced by the method described in JP-A No. 2000-80068 and JP-A No. 2011-177876. it can. As one of the methods, a method of producing by the following method according to the following reaction formula [Chemical Formula 14] can be mentioned.
That is, oxime compound 1 is obtained by reacting ketone body 1-1 with nitrite in the presence of hydrochloric acid. In a dimethyl sulfoxide solvent, the oxime ester compound 1 and the ketone body 1-2 are reacted in the presence of potassium carbonate, hydroxylamine is further reacted in the presence of hydrochloric acid, and the acid anhydride 1-1 or the acid chloride 1- By reacting 1 and acid anhydride 1-2 or acid chloride 1-2, the oxime ester compound of the present invention represented by the above general formula (III) can be produced. The following is an example when L ^{1 to} L ³ are hydrogen atoms.

（式中、Ｒ¹、Ｒ²、Ｒ²¹、Ｒ²²及びＺ⁵は一般式（ＩＩＩ）と同じである。）

(In the formula, R ¹ , R ² , R ²¹ , R ²² and Z ⁵ are the same as those in the general formula (III).)

The method for producing the oxime ester compound of the present invention represented by the general formula (IV) is not particularly limited. For example, the oxime ester compound can be produced by the methods described in JP-A Nos. 2000-80068 and 2011-178777. it can. As one of the methods, a method of producing by the following method according to the following reaction formula [Chemical Formula 15] can be mentioned.
That is, the oxime compound 2 is obtained by reacting the ketone body 2-1 with hydroxylamine in the presence of hydrochloric acid. By reacting the oxime compound 2 with an acid anhydride 2-1 or an acid chloride 2-1, an oxime ester compound 2-1 is obtained. The oxime ester compound 2-2 is obtained by reacting the oxime ester compound 2-1 and the ketone body 2-2 in the presence of potassium carbonate in a dimethyl sulfoxide solvent. Oxime ester compound 2-3 is obtained by reacting oxime ester compound 2-2 with hydroxylamine in the presence of hydrochloric acid. The oxime ester compound of the present invention represented by the above general formula (IV) can be produced by reacting the oxime ester compound 2-3 with the acid anhydride 2-2 or the acid chloride 2-2.

（式中、環Ａ、Ｒ²、Ｒ³、Ｒ²¹、Ｒ²²、Ｚ⁵及びｍは一般式（ＩＶ）と同じである。）

(In the formula, ring A, R ² , R ³ , R ²¹ , R ²² , Z ⁵ and m are the same as those in formula (IV).)

The method for producing the oxime ester compound of the present invention represented by the general formula (V) is not particularly limited. For example, the oxime ester compound can be produced by the methods described in JP-A Nos. 2000-80068 and 2011-178777. it can. As one of the methods, a method of producing by the following method according to the following reaction formula [Chemical Formula 16] can be mentioned.
That is, a ketone body 3-2 is obtained by reacting the ketone body 3-1 and the halide 3 in the presence of potassium carbonate in a dimethyl sulfoxide solvent. The oxime compound 3 is obtained by reacting the ketone body 3-2 with a nitrite in the presence of hydrochloric acid. By reacting the oxime compound 3 with an acid anhydride 3-1 or an acid chloride 3-1, an oxime ester compound 3-1 is obtained. The oxime ester compound 3-1 and hydroxyamine are reacted in the presence of hydrochloric acid to obtain the oxime ester compound 3-2. The oxime ester compound of the present invention represented by the general formula (V) can be produced by reacting the oxime ester compound 3-2 with an acid anhydride 3-2 or an acid chloride 3-2.

（式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵は一般式（Ｖ）と同じである。）

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ are the same as those in the general formula (V).)

The method for producing the oxime ester compound of the present invention represented by the above general formula (VI) is not particularly limited. For example, JP-A 2000-80068, JP-A 2011-177876 and JP-T 2010-538060 Can be produced by the method described in Japanese Patent Publication. As one of the methods, a method of producing by the following method according to the following reaction formula [Chemical Formula 17] can be mentioned.
That is, oxime compound 4 is obtained by reacting ketone body 4 and nitrite in the presence of hydrochloric acid. By reacting the oxime compound 4 with acid chloride 4-1 and acid chloride 4-2, the oxime ester compound of the present invention represented by the general formula (VI) can be produced.

（式中、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は一般式（ＶＩ）と同じである。）

(In the formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same as those in the general formula (VI).)

  The novel oxime ester compound of the present invention described above is useful as a photopolymerization initiator.

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

  The photosensitive composition of the present invention contains the photopolymerization initiator of the present invention and a polymerizable compound having an ethylenically unsaturated bond as essential components, and a polymerizable compound having a group that imparts alkali developability as an optional component In addition, it contains a combination of components such as 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 photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride can be used. , Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic 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- Carboxypolycaprolactone mono (meth) acrylate has carboxy group and hydroxyl group at both ends Limer mono (meth) acrylate; 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 Cuxinate, 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 Containing vinyl monomers and vinyl epoxy compounds of polyepoxy compounds; A1, No. A2, No. A3, No. A4 etc. are mentioned.
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 photopolymerization initiator containing the oxime ester 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 polymerizable compound having a group imparting alkali developability is not particularly limited as long as it is soluble in an alkaline aqueous solution, and examples thereof include resins described in JP-A No. 2004-264414.

Examples of the polymerizable compound having a group imparting alkali developability include an acrylic ester copolymer, a phenol and / or cresol novolac epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy acrylate. Resins obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (VII) and a polybasic acid anhydride can be used.
Among these, a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (VII) and further causing a polybasic acid anhydride to act thereon is preferable.
Moreover, it is preferable that the polymeric compound which has the group which gives the said alkali developability 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（イ）、（ロ）若しくは（ハ）で表される置換基を表し、上記アルキリデン基はハロゲン原子で置換される場合もあり、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る場合もあり、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 substituent represented by the following (a), (b) or (c), wherein the alkylidene group may be substituted with a halogen atom, and R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are: 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, alkoxy group and alkenyl. The 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、Ｚ⁶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または無置換のフェニル基、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または無置換の炭素原子数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る場合もある。ｄは０〜５の整数である。）

(In the formula, Z ⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group substituted or unsubstituted by an alkoxy group having 1 to 10 carbon atoms, or an alkyl group or carbon having 1 to 10 carbon atoms. A substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms represented by an alkoxy group having 1 to 10 atoms, Y ¹ is 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, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, d is an integer of 0 to 5)

（式中、Ｙ²及びＺ⁷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−で中断される場合もあり、Ｚ⁷は、隣接するＺ⁷同士で環を形成する場合もあり、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 ⁷ 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 also be interrupted by -O- or -S-, Z ⁷ , May also form a ring with the adjacent Z ⁷ to 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 to 4 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 photosensitive composition of the present invention, is a polymerization having the photopolymerization initiator of the present invention and an ethylenically unsaturated bond as essential components. And a polymerizable compound having a group that imparts alkali developability, 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 polymerizable compound having a group imparting alkali developability may be the same compound, may be different, or may be used alone. Two or more kinds can be used in combination.

  In order to improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound is further added together with the polymerizable compound having a group imparting alkali developability. Can be used. The polymerizable compound having a group imparting alkali developability preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the use amount of the monofunctional or polyfunctional epoxy compound satisfies the acid value. It is preferable to select as follows.

  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 (IV) 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 photosensitive composition of the present invention, the content of the photopolymerization 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 the photosensitive composition of the present invention, the content of the polymerizable compound having an ethylenically unsaturated bond is preferably 30 to 99% by mass, and preferably 60 to 95% by mass in the photosensitive composition. Is more preferable.

  In particular, when the photosensitive composition of the present invention is a (colored) alkali-developable photosensitive resin composition, the content of the polymerizable compound having a group imparting alkali developability is the (colored) alkaline development of the present invention. In the type photosensitive resin composition, 1 to 20% by mass, particularly 3 to 12% by mass is preferable.

A solvent can be further added to the photosensitive composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing each of the above-described components (the photopolymerization initiator of the present invention and a polymerizable compound having an ethylenically unsaturated bond) as necessary, such as methyl ethyl ketone, methyl amyl. Ketones such as ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol Ether solvents such as dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether Cellosolve solvents such as ethylene 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; Paraffinic solvents such as Luspirit, Swazol # 310 (Cosmo Matsuyama Petroleum), Solvesso # 100 (Exxon Chemical); Halogenated aliphatic carbonization such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane Hydrogenated solvent; Halogenated aromatic hydrocarbon solvent such as chlorobenzene; Carbitol solvent; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N, N-dimethylformamide; -Methylpyrrolidone; dimethyl sulfoxide; water etc. are mentioned, These solvents can be used as 1 type, or 2 or more types of mixed solvents.
Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable in the photosensitive composition because the compatibility between the resist and the photopolymerization initiator is good.

  The photosensitive composition of the present invention (particularly the alkali-developable photosensitive resin composition) 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; 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 photosensitive composition of the present invention, the content of the coloring material is preferably 50 to 350 parts by mass, more preferably 100 to 250 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. Part.

The photosensitive 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 photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. 800 parts by mass. 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.

  A dispersing agent for dispersing a colorant and / or an inorganic compound can be added to the photosensitive composition of the present invention. 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 photosensitive composition of this invention, another photoinitiator can be used together with the oxime ester compound of this invention. As other photopolymerization initiators that can be used in combination, conventionally known compounds can be used. For example, benzophenone, phenylbiphenylketone, 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-butyl Tylbenzoyltrichloromethane, 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, PZ-408 (manufactured by ADEKA), IRGACUR 369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), benzoyl peroxide, compounds represented by the following general formulas (VIII) to (X), and the like. When used, the amount used is preferably not more than 1 mass times the amount used of the oxime ester compound of the present invention. In addition, these photoinitiators can be used 1 type or in combination of 2 or more types.

（式中、Ｒ¹、Ｒ²及びＲ⁴は、上記一般式（Ｉ）と同じであり、Ｙ³は、ハロゲン原子又はアルキル基を表し、ｎは０〜５の整数である。）

(In the formula, R ¹ , R ² and R ⁴ are the same as those in the general formula (I), Y ³ represents a halogen atom or an alkyl group, and n is an integer of 0 to 5.)

（式中、Ｒ¹、Ｒ²及びＲ⁴は、上記一般式（Ｉ）と同じであり、Ｙ³及びｎは上記一般式（VIII）と同じであり、Ｒ’¹及びＲ’²は、Ｒ¹と同じであり、Ｒ’⁴はＲ⁴と同じであり、Ｙ’³はＹ³と同じであり、Ｚ⁸は酸素原子又は硫黄原子を表し、Ｚ⁹はジオール残基又はジチオール残基を表す。）

(Wherein R ¹ , R ² and R ⁴ are the same as those in the general formula (I), Y ³ and n are the same as those in the general formula (VIII), and R ′ ¹ and R ′ ² are The same as R ¹ , R ′ ⁴ is the same as R ⁴ , Y ′ ³ is the same as Y ³ , Z ⁸ represents an oxygen atom or a sulfur atom, and Z ⁹ represents a diol residue or a dithiol residue. Represents.)

（式中、Ｒ¹、Ｒ²及びＲ⁴は、上記一般式（Ｉ）と同じであり、Ｙ³及びｎは、上記一般式（VIII）と同じであり、Ｚ¹⁰は酸素原子、硫黄原子又はセレン原子を表し、環Ｂは複素環基を表し、ｔは０〜５の整数であり、ｕは０又は１である。）

(In the formula, R ¹ , R ² and R ⁴ are the same as those in the general formula (I), Y ³ and n are the same as those in the general formula (VIII), and Z ¹⁰ is an oxygen atom or a sulfur atom. Or represents a selenium atom, ring B represents a heterocyclic group, t is an integer of 0 to 5, and u is 0 or 1.)

  In addition, the photosensitive 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 a foaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.

  In the photosensitive composition of the present invention, an optional component other than the polymerizable compound having an ethylenically unsaturated bond and the oxime ester compound of the present invention (provided that the other photopolymerization initiator and a group imparting alkali developability are included). The amount of the polymerizable compound, inorganic compound (filler), coloring material and solvent excluded) is appropriately selected according to the purpose of use and is not particularly limited. However, the polymerization having the ethylenically unsaturated bond is preferable. The total amount is 50 parts by mass or less with respect to 100 parts by mass of the active compound.

Moreover, in the photosensitive composition of this invention, the characteristic of hardened | cured material can also be improved by using another organic polymer with the polymeric compound which has the said 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.

  In the photosensitive composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine and the like can be further used in combination.

  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 photosensitive composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic. It can be applied on a supporting substrate such as. 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.

  Further, as an energy ray light source used for curing the photosensitive composition of the present invention, 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, High electromagnetic wave energy, electron beam, X-ray, radiation, etc. having a wavelength of 2000 angstrom to 7000 angstrom obtained from carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. Although energy rays can be used, preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, or the like that emits light having a wavelength of 300 to 450 nm.

  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 photosensitive 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 personal digital assistant, a digital camera; Color filter of image sensor; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photoresist for electronics; Electroplating resist; Solder resists; resists for manufacturing color filters for various 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 Materials; solder resists; magnetic recording materials; micromechanical parts Optical switch; Plating mask; Etching mask; Color test system; Glass fiber cable coating; Screen printing stencil; Material for producing three-dimensional objects by stereolithography; Holographic recording material; Image recording material; Decolorization material; Decolorization material for image recording material; Decolorization material for image recording material using microcapsules; Photoresist material for printed wiring board; Photoresist material for UV and visible laser direct image system; It can be used for various applications such as a photoresist material or a protective film used for forming a dielectric layer in the sequential lamination of printed circuit boards, and the application is not particularly limited.

  The photosensitive composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive 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 photosensitive composition of the present invention on a substrate, and (2) irradiation of the coating film with radiation through a mask having a predetermined pattern shape. (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) photosensitive 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 a partition for an inkjet color filter. As the ink repellent agent, a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.

  An optical element is formed by a method in which a partition formed from the photosensitive composition of the present invention partitions an image to be transferred, and droplets are applied to the recessed portions on the partitioned image to be transferred by an ink jet method to form an image region. 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 photosensitive composition of the present invention is also used as a composition for a protective film or insulating film, and is a monofunctional or bifunctional compound containing an ultraviolet absorber, an alkylated modified melamine and / or an acrylic modified melamine, and an alcoholic hydroxyl group in the molecule. (Meth) acrylate monomer and / or silica sol.

As the photosensitive 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 photopolymerizable ethylenically unsaturated bond in one molecule,
(C) an epoxy compound, and (D) a photopolymerization initiator,
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 to contain a compound represented by the above general formula (I) as a photopolymerization initiator of the component.

  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 photosensitive 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.

Example 1 Compound No. 1 54 production
<Step 1> Under a nitrogen oxime stream, 3.14 g (10.0 mmol) of 1-butanone-2-ene, 1- {4- [4- (2-hydroxyethoxy) phenylthio] phenyl} was dissolved in 200 mL ethanol. Then, t-butyl nitrite (50.0 mmol) dissolved in 30 mL of purified water was added dropwise in the presence of hydrochloric acid. Stir for 1.5 hours and pour into purified water. The precipitate was filtered and washed with purified water to obtain 2.90 g of an oxime body.
<Step 2> Acetylation 2.90 g (8.0 mmol) of the oxime obtained in Step 1 above was dissolved in 50 mL of methylene chloride, and 4.05 g (40.0 mmol) of triethylamine was added dropwise. Subsequently, 3.14 g (40.0 mmol) of acetyl chloride was added dropwise while cooling. After reacting at room temperature for 2 hours, it was washed 3 times with purified water. The organic layer was dried and desolvated using anhydrous sodium sulfate. The product was purified using a column and the target compound No. 2.20 g of 54 was obtained.

Compound No. Analytical analysis of 54: (Measured value C: 59.5%, H: 5.9%, N: 5.7%, S: 6.7%, Theoretical value C 59.00% :, H 5.78%: , N: 5.73%, S: 6.56%)
Mass: 488

[Example 2] Alkali-developable photosensitive resin composition No. Production of 1 <Step 1> Production of alkali-developable resin In a reaction vessel, a bisphenolfluorene-type epoxy resin represented by the general formula (VII) (X ¹ is a group represented by (b), epoxy equivalent 231 ) 184 g, acrylic acid 58 g, 2,6-di-tert-butyl-p-cresol 0.26 g, tetra-n-butylammonium bromide 0.11 g and propylene glycol-1-monomethyl ether-2-acetate 23 g, Stir at 120 ° C. for 16 hours. The reaction solution was cooled to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. After stirring for 4 hours, 20 g of tetrahydrophthalic anhydride was further added, and after stirring at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, propylene glycol 90 g of -1-monomethyl ether-2-acetate was added to obtain a target propylene glycol-1-monomethyl ether-2-acetate solution as an alkali developing resin No. 1 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g) was obtained.
<Step 2> Alkali-developable photosensitive resin composition No. Preparation of Alkali Developable Resin No. 1 1 10.7 g, dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toa Gosei Co., Ltd.) 2.7 g, surfactant FZ-2122 (manufactured by Nihon Unicar) 1.2 g cyclohexanone 1% solution, propylene glycol 2.7 g of -1-monomethyl ether-2-acetate and 12.6 g of cyclohexanone were mixed and No. 54 of 0.07 g was added and stirred well, and the alkali-developable photosensitive resin composition no. 1 was obtained.
[Comparative Example 1] Production of Comparative Alkali-Developable Photosensitive Resin Composition 1 Compound No in Example 1 <Step 2 in Example 2 except that 54 is replaced with ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) The comparative alkali-developable photosensitive resin composition 1 was obtained in the same manner as above.

<Evaluation of transmittance>
Alkali-developable photosensitive resin composition No. 1 and comparative alkali-developable photosensitive resin composition 1 were evaluated for transmittance as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 800 rpm, 6 seconds), and prebaked at 90 ° C. for 90 seconds using a hot plate. The light source was exposed to 150 mJ / cm ² using a high-pressure mercury lamp as a light source, and post-baked at 230 ° C. for 30 minutes using an oven. The transmittance at 380 nm was measured using an absorptiometer. The results are shown in Table 1.
<Sensitivity evaluation>
Alkali-developable photosensitive resin composition No. 1 and the sensitivity of the comparative alkali-developable photosensitive resin composition 1 were evaluated in the following three stages. That is, the line width of the formed pattern, a case where the exposure amount when exceeding the mask opening line width was 60 mJ / cm ² ○, the case was ^{80mJ / cm 2 △, 100 mJ} / cm 2 When it was, it was set as x. The results are shown in Table 1.
<Outgassing>
Alkali-developable photosensitive resin composition No. 1 and the comparative alkali-developable photosensitive resin composition 1 were subjected to an outgas test as follows. Specifically, a colored alkali-developable photosensitive resin composition is spin-coated (500 rpm, 7 seconds) on a glass substrate, pre-baked at 90 ° C. for 90 seconds using a hot plate, and a high-pressure mercury lamp is used as the light source. Exposed to 100 mJ / cm ² . About 3 mg of this membrane was scraped, and the outgassing property was evaluated from the weight reduction rate when held at 230 ° C. for 30 minutes by TG-DTA (manufactured by Seiko Instruments Inc.). The results are shown in Table 1.

  From the results in Table 1, the alkali-developable photosensitive resin composition no. It was found that No. 1 is a composition that exhibits a higher transmittance than the comparative alkali-developable photosensitive resin composition 1, has a good sensitivity, and has the effect of reducing outgas.

Claims (7)

The oxime ester compound represented by the following general formula (I) or (II).

(Wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN; R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; Represents an atom, 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 heterocyclic group having 2 to 20 carbon atoms, R ¹¹ , R The hydrogen atom of the substituent represented by ¹² and R ¹³ is OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR ²² —OCOR ²³ , —C ( ═N—OR ²¹ ) —R ²² , —C (═N—OCOR ²¹ ) —R ²² , CN, halogen atom, or COOR ²¹ ,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, 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. The hydrogen atom of the substituent represented by the number 2-20 heterocyclic group represented by R ²¹ , R ²² and R ²³ may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,
The alkylene part of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, — NR ²⁴ COO—, —OCONR ²⁴ —, —SCO—, —COS—, —OCS—, or —CSO— may be interrupted 1 to 5 times, and R ²⁴ is a hydrogen atom or a carbon atom number of 1 to 20 An alkyl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R ¹¹ , R ¹² , R ¹³ , R ²¹ , The alkyl part of the substituent represented by R ²² and R ²³ may have a branched side chain or may be a cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ are combined together. May form a ring,
R ³ , L ¹ , L ² and L ³ are R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ^{11 represents} a hydroxyl group, a nitro group, CN or a halogen atom, and L ¹ and R ³ , R ³ and L ^2, and L ² and L ³ may form a ring together to form a ring, R ¹⁴ , R 3 ¹⁵ and R ¹⁶ are a hydrogen atom or 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 heterocyclic group having 2 to 20 carbon atoms. R ⁴ represents a hydrogen atom, 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 heterocyclic ring having 2 to 20 carbon atoms. It represents a group, the alkyl moiety of the group represented by R ^4, May be the case or cyclic alkyl have岐側chain, hydrogen atoms in the group represented by R ⁴ may further ^{R 21, OR 21, COR 21} , SR 21, NR 22 R 23, CONR 22 R 23, - ^{NR 22 -OR 23, -NCOR 22 -OCOR} 23, NR 22 COR 21, OCOR 21, COOR 21, -C (= N-OR 21) -R 22, -C (= N-OCOR 21) -R 22, SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN, halogen atom, or COOR ²¹ may be substituted, and X is a direct bond, CO, or the following general formula (IA) Represents the group represented. )

(In the formula, Z ¹ and Z ² are a bond, a single bond, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms. Or a heterocyclic group having 2 to 20 carbon atoms,
The alkylene part of the bond represented by Z ¹ and Z ² is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ COO—, —OCONR ²⁴ —, —SCO. It may be interrupted 1 to 5 times by —, —COS—, —OCS— or —CSO—, and the alkylene part of the bond represented by Z ² may be a branched side chain or a cyclic alkylene. is there.
R ⁵ represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (I). )

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ represent the above general formulas) Same as formula (I),
R ⁹ represents OH, COOH or a group represented by the following general formula (II-A),
Y represents an oxygen atom, a sulfur atom, a selenium atom, CR ³¹ R ³² , CO, NR ³³ or PR ³⁴ , α represents an integer of 1 to 10, and R ³¹ , R ³² , R ³³ and R ³⁴ represent Each independently represents 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;
The alkyl part of the substituent represented by R ³¹ , R ³² , R ³³ and R ³⁴ may have a branched side chain or a cyclic alkylene, and R ³¹ , R ³² , R ³³ and R ³⁴ may be Each may independently form a ring together with one of the adjacent benzene rings. )

(In the formula, Z ³ is a bond, and represents —O—, —S—, —NR ²² —, —NR ²² CO—, —SO ₂ —, —CS—, —OCO— or —COO—. Represent,
Z ⁴ is a bond and is 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, which is substituted with 1 to 3 R ^10. Or a heterocyclic group having 2 to 20 carbon atoms,
The alkylene part of the bond represented by Z ⁴ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ COO—, —OCONR ²⁴ —, —SCO—, — It may be interrupted 1 to 5 times by COS-, -OCS- or -CSO-, and the alkylene part of the bond represented by Z ⁴ may have a branched side chain or a cyclic alkylene, and R ¹⁰ represents OR ⁴¹ , SR ⁴¹ , CONR ⁴² R ⁴³ , NR ⁴² COR ⁴³ , OCOR ⁴¹ , COOR ⁴¹ , SCOR ⁴¹ , OCSR ⁴¹ , COSR ⁴¹ , CSOR ⁴¹ , CN or a halogen atom, R ⁴¹ , R ⁴² and R ⁴³ independently represents 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 R ⁴¹ , R ⁴² and A of the substituent represented by R ⁴³ The alkyl moiety may have a branched side chain or may be a cyclic alkylene, and R ⁴² and R ⁴³ may together form a ring, and a represents an integer of 1 to 3. R ²² and R ²⁴ are the same as those in the general formula (I). )   A photopolymerization initiator containing the oxime ester compound according to claim 1.   A photosensitive composition comprising the photopolymerization initiator according to claim 2 containing a polymerizable compound.   A photosensitive composition, wherein the polymerizable compound according to claim 3 is a polymerizable compound having an ethylenically unsaturated bond.   An alkali-developable photosensitive resin composition comprising the photosensitive composition according to claim 3 and a polymerizable compound having a group imparting alkali developability.   A colored alkali-developable photosensitive resin composition obtained by further adding a coloring material to the alkali-developable photosensitive resin composition according to claim 5. The photosensitive composition according to any one of claims 3 and 4, the alkali-developable photosensitive resin composition according to claim 5, or the colored alkali-developable photosensitive resin composition according to claim 6. A cured product that is irradiated with energy rays.