JP6539476B2 - Oxime ester compound and photopolymerization initiator containing the compound - Google Patents

Description

  The present invention provides a novel oxime ester compound useful as a photopolymerization initiator to be used in a photosensitive composition, a photopolymerization initiator containing the compound, and a polymerizable compound 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 irradiation with energy rays (light), so a photocurable ink , Photosensitive printing plates, various photoresists, etc.

The use of an oxime ester compound is proposed in the following Patent Documents 1 to 3 as a photopolymerization initiator used for the photosensitive composition.
However, among the oxime ester compounds described in the above-mentioned patent documents, the oxime ester compound which has satisfactory sensitivity has a low transmittance in the visible light region, and a desired color can not be obtained with a color filter (especially, the protective film Such light-sensitive compositions and resists for color filters using blue pigments or dyes have reduced lightness and color purity if compounds having absorption at 380 to 450 nm are mixed), and also visible light region The oxime ester compound having a high transmittance of 1 has a problem that the sensitivity is not sufficiently satisfactory, and a photopolymerization initiator having both properties has been required.

  In addition, colored alkaline developable photosensitive resin compositions containing coloring materials such as color filters are required to have high sensitivity and high solubility in organic solvents, and high concentration of photopolymerization initiators in resists. It is necessary to However, the high concentration photopolymerization initiator causes the generation of a residue due to the deterioration of the developability, the contamination of the photomask and the heating furnace with the sublimate, and the like.

Japanese Patent Application Laid-Open No. 2000-80068 Japanese Patent Publication No. 2006-516246 specification International Publication 2013/008652

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

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

  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 are each independently R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each independently hydrogen) R ¹¹ represents 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 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 ( NN-OR ²¹ ) -R ²² , -C (= N-OCOR ²¹ ) -R ²² , CN, a halogen atom, or COOR ²¹ may be substituted,
R ²¹ , R ²² and R ²³ each independently represent 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 And the hydrogen atom of the substituent 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 moiety 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- by sometimes be interrupted 1 to 5 times, R ²⁴ represents a hydrogen atom, carbon atom 20 R ¹¹ , R ¹² , R ¹³ , R ²¹ , 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, The alkyl moiety of the substituent represented by R ²² and R ²³ may be branched side chain or cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ may be respectively taken together. R ³ may form a ring, and R ³ represents 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 together form a ring, R ¹⁴ and R ^{15 respectively.} And R ¹⁶ is 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, a hydroxyl group, a nitro group, CN, might also be substituted by a halogen atom, or COOR ^21, X is a direct bond, a CO or the following formula (I-A) Represents a group to be 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。）

(Wherein, Z ¹ and Z ^{2 each} represents a bond, and are 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 moiety of the bond represented by Z ¹ and Z ² 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 moiety of the bond represented by Z ² may be branched side chain or 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 in the above 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 each} represent the above general formula) 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, R ³¹ , R ³² , R ³³ and R ³⁴ represent And 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 moiety of the substituent represented by R ³¹ , R ³² , R ³³ and R ³⁴ may be a branched side chain or cyclic alkylene, and R ³¹ , R ³² , R ³³ and R ³⁴ may be Each of them may form a ring together with either of 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。）

(Wherein, Z ³ represents a bond, and is —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, which is substituted by 1 to 3 R ¹⁰ , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms Or a heterocyclic group having 2 to 20 carbon atoms,
Alkylene moiety of bond represented by Z ⁴ is, -O -, - S -, - COO -, - OCO -, - NR 24 -, - NR 24 COO -, - OCONR 24 -, - SCO -, - In some cases, the alkylene moiety of the bond represented by Z ⁴ may be a branched side chain or may be a cyclic alkylene, which may be interrupted 1 to 5 times by COS-, -OCS- or -CSO-, 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 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, 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 in the above general formula (I). )

The present invention also provides a photosensitive composition comprising the above-mentioned photopolymerization initiator and a polymerizable compound having an ethylenically unsaturated bond.
The present invention also provides an alkali-developable photosensitive resin composition comprising the above-described photosensitive composition and a polymerizable compound having a group that imparts alkali developability.
The present invention also provides a colored alkali-developable photosensitive resin composition, which is obtained by adding a coloring material to the above-mentioned alkaline-developable photosensitive resin composition.

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

  The oxime ester compound of the present invention is excellent in stability, low in sublimation, excellent in developability, high in visible light transmittance, high in organic solvent solubility, bright line such as 365 nm (i-line), etc. It is useful as a photopolymerization initiator to generate radicals efficiently and to be used for the photosensitive composition.

  Hereinafter, the oxime ester compound of the present invention and the 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). Although the geometric isomer by the double bond of oxime exists in this oxime ester compound, these are not distinguished.
That is, in the present 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 embodiments of the compound described later And the compounds represented by the general formula (VI) and the exemplified compounds thereof represent a mixture or both of both, and are not limited to the structures showing the isomers.

R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 in the} above general formula (I) and the above 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 For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, Isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclic Hexyl ethyl, and the like.

R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 in the} above general formula (I) and the above 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 For example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted by one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl and the like can be mentioned.

R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 in the} above general formula (I) and the above 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 are arylalkyl groups having 7 to 30 carbon atoms As such, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like can be mentioned.

R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ^{24 in the} above general formula (I) and the above general formula (II) And the heterocyclic group having 2 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²² and R ²⁴ is, for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole 5- to 7-membered heterocyclic rings such as -2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazil, morpholinyl and the like are preferably mentioned.

Rings which R ¹² and R ^{13 in} the above general formula (I), R ²² and R ²³ , and in the above general formula (II), R ⁴² and R ⁴³ can form together, and R ³¹ and R ³¹ Examples of the ring which may be formed together with the adjacent benzene ring of ³² and R ³³ and R ³⁴ include, for example, cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring 5 to 7 membered rings are preferably mentioned.

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

Examples of the alkyl group having 1 to 20 carbon atoms which is substituted with R ¹⁰ 1-3, 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 thereof include alkylene groups such as pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tridecylene, tetradecylene, pentadecylene, ethane-1,1-diyl, propane-2,2-diylyl and the like.

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

The aryl alkyl group having 7 to 30 carbon atoms which is substituted with R ¹⁰ 1-3, for example, when a is 1, an aryl alkylene group such as a linking group represented by Chemical Formula 5] Be

（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-thiazolediyl, 2,5-benzofuranyl, 2,5 And divalent heterocyclic groups such as -benzothiophenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazolediyl, 2,5-benzoxazolediyl and the like.

Z ^1, Z Examples of alkyl group having 1 to 20 carbon atoms is a bond, represented by ² and Z ^5, represented by Z ^4, carbon atoms 1 to be replaced by a number of R ¹⁰ Examples of the case where a in the alkyl group of 20 is 1 include the same groups as those 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 , an aryl group having 6 to 30 carbon atoms which is substituted with a number of R ¹⁰ is represented by Z ^4, a heterocyclic group each of a arylalkyl group and C2-20 having 7 to 30 carbon atoms Examples of the case 1 include the same groups as those mentioned above.

Also, a halogen atom represented by R ¹⁰ in the general formula (II), and a halogen atom represented by R ³ , L ¹ , L ² and L ³ in the general formula (I), R ⁴ , the ^{R 11, R 12, R 13} , R 21, halogen atom be substituted R ²² and R ^23, fluorine, chlorine, bromine, and iodine.

Substituents represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the general formula (I) or (II), and in the general formula (I) or (II) And the alkylene moiety of the bond represented by Z ¹ , Z ² , Z ⁴ and Z ⁵ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, —NR ²⁴ CO—, ^{-NR 24 COO -, - OCONR 24} -, - SCO -, - COS -, - OCS- or -CSO- by sometimes be interrupted 1 to 5 times, this time interrupting linking groups one or two It may be the above groups, and in the case of groups which can be interrupted continuously, there may be cases where two or more are interrupted successively.
Also, in the above general formula (I) or (II), a substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ , and the above general formula (I) or (II) Among them, the substituents represented by R ³¹ , R ³² , R ³³ and R ³⁴ , the bonds represented by Z ² , Z ⁴ and Z ⁵ , and the substituents represented by R ⁴¹ , R ⁴² and R ^43. The alkyl (alkylene) portion of the group may be branched side chain or cyclic alkyl (cyclic alkylene).

  Among the oxime ester compounds of the present invention, the compounds represented by the following general formula (III), general formula (IV), general formula (V) and general formula (VI) are excellent in stability and low in sublimation , Excellent in developability, high transmittance in the visible light region, high solubility in organic solvents, high effect of efficiently generating radicals for bright 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。）

(Wherein, Z ⁵ represents 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 And the alkylene moiety of the bond represented by Z ⁵ represents -O-, -S-, -COO-, -OCO-, -NR ^24- , -NR ²⁴ COO-, -OCONR ^{24 -, - SCO -, -} COS -, - OCS- or -CSO- by sometimes be interrupted 1 to 5 times, or when the cyclic alkylene portion of the bond represented by Z ⁵ have a branched side chain It may be alkylene, and R ¹ , R ² , R ²¹ , R ²² , R ²⁴ , L ¹ , L ² and L ³ are as defined in general 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。）

(Wherein, ring A represents a 5-membered or 6-membered hydrocarbon ring having 1 to 20 carbon atoms, and a hydrogen atom in ring A further represents 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 And R 2 may be substituted with a halogen atom or COOR ^21. When there is a plurality of R ^{21 in the} formula, R ²¹ may be the same or different, and R ² , R ³ , R ²¹ , R ²² , R ²³ , L ¹ , L ² , L ³ and Z ⁵ are as defined in the general 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。）

(Wherein, R ¹ , R ² , R ⁴ , R ⁵ , L ¹ , L ² and L ³ are as defined 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。）

(Wherein, R ⁶ , R ⁷ , R ⁸ and R ⁹ are as defined in the general formula (II))

Examples of the five-membered ring in the C1-C20 five-membered ring or six-membered hydrocarbon represented by ring A in the general formula (IV) include a cyclopentyl ring, a methylcyclopentyl ring and an ethylcyclopentyl ring. The six-membered ring includes a cyclohexyl ring, a methylcyclohexyl ring, an ethylcyclohexyl ring, a phenyl group, a benzyl group and a tolyl group. The hydrogen atom in ring A further includes 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 , when it is substituted for ring A, including the number of carbon atoms in these substituents The carbon atom number is "1 to 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 each an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms The case is preferred because of its good developability, and particularly preferred is a methyl group, an ethyl group or a phenyl group. Further preferred because when Z ⁵ in the general formula (III) is a methylene, ethylene or phenylene is easy to synthesize.

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 these, a methyl group, an ethyl group or a phenyl group is particularly preferable. Further preferred because when Z ⁵ in the above general formula (IV) is a methylene, ethylene or phenylene is easy to synthesize.

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, developability is good. Among these, a methyl group, an ethyl group or a phenyl group is particularly preferable.
Further preferred because when Z ⁵ in the general formula (V) is a methylene, ethylene or phenylene is easy to synthesize.

Among the oxime ester compounds of the present invention, 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, development is performed It is preferable from the viewpoint of good properties, and particularly preferred is a methyl group, an ethyl group or a phenyl group.

  Preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (III) include the following compound No. 1 to No. 10 can be mentioned. However, the present invention is not limited at all by the following compounds. In the following chemical formulas, "Me" represents a methyl group, and "Ph" represents a phenyl group.

  As preferable specific examples of the oxime ester compound of the present invention represented by the above general formula (IV), the following compound Nos. 11 to No. There are thirty. However, the present invention is not limited at all by the following compounds. In the following chemical formulas, "Me" represents a methyl group, and "Ph" represents a phenyl group.

  As preferable specific examples of the oxime ester compound of the present invention represented by the above general formula (V), the following compound Nos. 31 to No. 45 can be mentioned. However, the present invention is not limited at all by the following compounds. In the following chemical formulas, "Me" represents a methyl group, and "Ph" represents a phenyl group.

  As preferable specific examples of the oxime ester compound of the present invention represented by the above general formula (VI), the following compound Nos. 46-No. 57 can be mentioned. However, the present invention is not limited at all by the following compounds. In the following chemical formulas, "Me" represents a methyl group, and "Ph" represents a phenyl group.

Although 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-2000-80068 and JP-A-2011-178776. it can. As one of the methods, a method of producing by the following method can be mentioned according to the following reaction formula.
That is, the oxime compound 1 is obtained by reacting the ketone body 1-1 with a nitrite in the presence of hydrochloric acid. The oxime ester compound 1 and ketone body 1-2 are reacted in the presence of potassium carbonate in a dimethylsulfoxide solvent, and hydroxylamine is further reacted in the presence of hydrochloric acid, and further acid anhydride 1-1 or 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 in which 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。）

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

The method for producing the oxime ester compound of the present invention represented by the above general formula (IV) is not particularly limited. For example, it is produced by the method described in JP-A-2000-80068 and JP-A-2011-178776. it can. As one of the methods, the method of manufacturing by the following method is mentioned according to the following reaction formula.
That is, the oxime compound 2 is obtained by reacting the ketone body 2-1 with hydroxylamine in the presence of hydrochloric acid. The oxime ester compound 2-1 is obtained by reacting the acid anhydride 2-1 or the acid chloride 2-1 with the oxime compound 2. 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. The oxime ester compound 2-3 is obtained by reacting the oxime ester compound 2-2 with hydroxylamine in the presence of hydrochloric acid. By reacting the acid ester 2-2 or the acid chloride 2-2 with the oxime ester compound 2-3, the oxime ester compound of the present invention represented by the above general formula (IV) can be produced.

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

The method for producing the oxime ester compound of the present invention represented by the above general formula (V) is not particularly limited. For example, it is produced by the method described in JP-A-2000-80068 and JP-A-2011-178776. it can. One of the methods is a method of manufacturing by the following method according to the following reaction formula.
That is, ketone body 3-1 and halide 3 are reacted in the presence of potassium carbonate in a dimethylsulfoxide solvent to obtain ketone body 3-2. The oxime compound 3 is obtained by reacting the ketone body 3-2 with a nitrite in the presence of hydrochloric acid. The oxime ester compound 3-1 is obtained by reacting the acid anhydride 3-1 or the acid chloride 3-1 with the oxime compound 3. The oxime ester compound 3-2 is obtained by reacting the oxime ester compound 3-1 with hydroxylamine in the presence of hydrochloric acid. By reacting the acid ester 3-2 or the acid chloride 3-2 with the oxime ester compound 3-2, the oxime ester compound of the present invention represented by the above general formula (V) can be produced.

（式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵は一般式（Ｖ）と同じである。）

(Wherein, R ¹ , R ² , R ⁴ and R ⁵ are the same as 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, but, for example, JP-A-2000-80068, JP-A-2011-178776 and JP-A-2010-538060 It can manufacture by the method as described in the gazette. As one of the methods, a method of producing by the following method according to the following reaction formula of [Chemical formula 17] can be mentioned.
That is, the oxime compound 4 is obtained by reacting the ketone 4 with a nitrite in the presence of hydrochloric acid. By reacting the acid chloride 4-1 and the acid chloride 4-2 with the oxime compound 4, the oxime ester compound of the present invention represented by the above 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。）

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

  The novel oxime ester compounds of the present invention described above are useful as photopolymerization initiators.

  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 of a polymerizable compound having an ethylenically unsaturated bond. The content of the oxime ester compound of the present invention in the photopolymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

  The photosensitive composition of the present invention contains, as essential components, the photopolymerization initiator of the present invention and a polymerizable compound having an ethylenically unsaturated bond, and as an optional component, a polymerizable compound having a group that provides alkali developability. And an inorganic compound, a coloring material, a solvent and the like in combination.

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 Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride and 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, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, ω- Having carboxy group and hydroxyl group at both ends of carboxypolycaprolactone mono (meth) acrylate etc. Lymer mono (meth) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or having one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; 2-hydroxyethyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate; A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (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, (meth ) Ethyl hexyl 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, trimethylolethane triol (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) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid 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, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid and biphenyl Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol, crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenyl maleimide, N -Unsaturated imides such as cyclohexyl maleimide; Indens such as indene and 1-methyl indene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyls Succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group The vinyl epoxy compounds of the contained vinyl monomers and polyepoxy compounds; A1, No. A2, No. A3, No. A4 etc. are mentioned.
Among these, mono (meth) acrylate of polymer having carboxy group and hydroxyl group at both ends, polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups, unsaturated one The photoinitiator which contains the oxime ester compound of this invention is suitable for the ester of a basic acid and polyhydric alcohol or polyhydric phenol.
These polymerizable compounds can be used alone or in combination of two or more, and when two or more are mixed and used, they are copolymerized in advance and used as a copolymer. May be

  The polymerizable compound having a group that gives the 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-2004-264414.

Further, as the polymerizable compound having a group giving the above alkali developability, a copolymer of acrylic acid ester, phenol and / or cresol novolac epoxy resin, polyphenylmethane type epoxy resin having a multifunctional epoxy group, epoxy acrylate A resin obtained by causing 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 can be used.
Among these, resins obtained by causing 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 on the epoxy compound are preferable.
Moreover, it is preferable that the polymeric compound which has 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 (i), (ro) or (ha), the above 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 of 1 to 5 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, an alkenyl group of 2 to 5 carbon atoms or a halogen atom, and the above alkyl group, alkoxy group and alkenyl group The group may be substituted by 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。）

(Wherein, Z ⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group substituted or unsubstituted with an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms or carbon C1-C10 substituted or unsubstituted cycloalkyl group is represented by C1-C10 alkoxy group, Y ¹ is C1-C10 alkyl group, C1-C10 alkoxy group, C2-10 alkenyl group or halogen atom is shown, and the above-mentioned alkyl group, alkoxy group and alkenyl group may be substituted by a halogen atom, and 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 each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms optionally substituted with a halogen atom. The aryl group of 6 to 20 carbon atoms which may be substituted with a halogen atom, the arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, substituted with a halogen atom; A C 6-20 arylalkenyl group, a C 7-20 arylalkyl group which may be substituted by a halogen atom, a C 2-20 hetero ring optionally substituted by 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 And the sum of the numbers r and s is an integer of 2 to 4.)

  As the above-mentioned unsaturated monobasic acid which acts on the above-mentioned epoxy compound, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl Acrylate malate, dicyclopentadiene malate, etc. may be mentioned.

  Moreover, as said polybasic acid anhydride made to act after making said unsaturated monobasic acid act, biphenyl tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanehydrotrimellitate, hexahydrophthalic anhydride Methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1, 2-dicarboxylic acid anhydride, trialkyl tet Anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

It is preferable that the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride be as follows.
That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl group of the unsaturated monobasic acid is added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct Preferably, the ratio of the number of acid anhydride structures of the polybasic acid anhydride to the number of pieces thereof is 0.1 to 1.0.
The reaction of the above epoxy compound, the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to 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, comprises, as an essential component, a photopolymerization initiator of the present invention and polymerization having an ethylenically unsaturated bond It contains an organic compound and a polymerizable compound having a group that gives alkali developability, and contains an optional component such as an inorganic compound, a coloring material, a solvent and the like in combination. Among the alkali-developable photosensitive resin compositions of the present invention, those containing a coloring material are particularly referred to as the colored alkaline-developable photosensitive resin compositions of the present invention.
The polymerizable compound having an ethylenically unsaturated bond described above and the polymerizable compound having a group providing an alkali developability described above may or may not be the same compound, and may be independent. Two or more types can also be used in combination.

  In order to adjust the acid value and improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention, a monofunctional or polyfunctional epoxy compound is further added together with a polymerizable compound having a group giving alkali developability. It can be used. It is preferable that the acid value of solid content is in the range of 5 to 120 mg KOH / g, and the used amount of the monofunctional or polyfunctional epoxy compound satisfies the above 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 glycidyl ether , 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 monoxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compound No. 1 E1, No. E2 etc. are mentioned.

When one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers are used as the above-mentioned polyfunctional epoxy compounds, it is possible to obtain a (coloring) alkali developable photosensitive resin composition having better characteristics. Because it can be
As the above-mentioned bisphenol type epoxy compound, in addition to the epoxy compound represented by the above general formula (IV), for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Further, as the above glycidyl ethers, 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.
In addition, 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, etc .; 3,4-epoxy-6-methyl; Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane and the like Compounds; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diamino acid Glycidyl amines such as phenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline, etc .; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5, 5-dimethylhydantoin, triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds etc. 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 preferably 1 relative to 100 parts by mass of the above-mentioned polymerizable compound having an ethylenically unsaturated bond. The amount is 70 to 70 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 5 to 30 parts by mass.

  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 more preferably 60 to 95% by mass, in the photosensitive composition. Is more preferred.

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

A solvent can be further added to the photosensitive composition of the present invention. As the solvent, usually, a solvent capable of dissolving or dispersing the above-mentioned respective components (the photopolymerization initiator of the present invention and the polymerizable compound having an ethylenically unsaturated bond, etc.) as necessary, for example, methyl ethyl ketone, methyl amyl Ketones, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol Ether solvents such as dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl acetate, ethyl lactate, dimethyl succinate, texanol ester solvents; ethylene glycol monomethyl ether Cellosolv solvents such as ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and 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 and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene and xylene; hexane Aliphatic hydrocarbon solvents such as heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffinic solvents such as LeSpirit, Swazor # 310 (Cosmo Matsuyama Petroleum Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic carbonization such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Hydrogen solvents; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; -Methyl pyrrolidone; dimethyl sulfoxide; water etc. may be mentioned, and these solvents can be used as one or more mixed solvents.
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 photosensitive composition because the compatibility between the resist and the photopolymerization initiator is good.

  Further, a coloring material may be further contained in the photosensitive composition of the present invention (in particular, the alkali-developable photosensitive resin composition) to obtain a colored (alkali-developable) photosensitive composition. Examples of the coloring material include pigments, dyes, natural dyes and the like. These coloring materials can be used alone or in combination of two or more.

Examples of the pigment include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthrone compounds, perinones Compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, lake pigments, furnace method, channel method or thermal Black obtained by the above method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared or coated with an epoxy resin, the carbon black previously dispersed in a solvent with a resin, and adsorbed with a resin of 20 to 200 mg / g, the carbon black subjected to an acid or alkaline surface treatment, an average With a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen content calculated from CO and CO ₂ in volatile components at 950 ° C. is 9 mg or more per 100 m ^{2 of} carbon black surface area; Graphite Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese system , Ferrocyanide Phosphate blue, bitumen, ultramarine, cerulian blue, pyridinium, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black, organic or inorganic such as amber Pigments can be used. These pigments may be used alone or in combination of two or more.

  Commercially available pigments can also be used as the pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 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, 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, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 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 and the like.

  Examples of the dyes include 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, and phthalocyanine dyes And dyes such as cyanine dyes, and the like, and these may be used as a mixture of two or more.

  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. It is a department.

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; layered clay minerals, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper and the like can be 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 1000 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. It is 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 a filler, an antireflective agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, an ink repellent agent, and the like.

  The photosensitive composition of the present invention may contain a dispersant for dispersing the colorant and / or the inorganic compound. The dispersing agent is not particularly limited as long as it can disperse and stabilize the coloring material or the inorganic compound, and a commercially available dispersing agent, for example, BYK series manufactured by Big Chemie Co., Ltd. can be used. In particular, a polymer dispersant comprising a polyester, polyether or polyurethane having a basic functional group, a nitrogen atom as a basic functional group, and a 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 mg KOH / g are preferably used.

  In the photosensitive composition of the present invention, other photopolymerization initiators can be used in combination with the oxime ester compound of the present invention. As other photopolymerization 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-morpholine-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-bu Ethyl benzoyl trichloromethane, 4-phenoxy benzoyl dichloromethane, methyl benzoyl formate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyryl) 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 , Camphor quinone, N-1414, N-1717, N-1919, PZ-408 (manufactured by Adeka), IRGACUR 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Corp.), benzoyl peroxide, compounds represented by the following general formulas (VIII) to (X), etc. When used, the amount used is preferably at most 1 mass times the amount used of the oxime ester compound of the present invention. In addition, these photoinitiators can be used combining 1 type or 2 types or more.

（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。）

(Wherein, R ¹ , R ² and R ⁴ are the same as in the above 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 the above general formula (I), Y ³ and n are the same as the above general formula (VIII), and R ′ ¹ and R ′ ² are It is the same as R ¹ , R ′ ⁴ is the same as R ⁴ , Y ′ ³ is the same as Y ³ , Z ⁸ is an oxygen atom or a sulfur atom, and Z ⁹ is 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。）

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

  In the photosensitive composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, etc .; a plasticizer; an adhesion promoter; a filler; Foaming agents; leveling agents; surface conditioners; antioxidants; ultraviolet light absorbers; dispersing aids; flocculants; catalysts; effect accelerators; crosslinking agents; and conventional additives such as thickeners can be added.

  In the photosensitive composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond and an optional component other than the oxime ester compound of the present invention (however, the other photopolymerization initiator described above, a group giving alkali developability) The use amount of the polymerizable compound, the inorganic compound (filler), the coloring material and the solvent is appropriately selected according to the purpose of use and is not particularly limited, but preferably, the polymerization having the above-mentioned ethylenic unsaturated bond 50 parts by weight or less based on 100 parts by weight of the organic compound.

Moreover, 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 for the photosensitive composition of this invention. 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 Polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin, etc. may be mentioned. Among them, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin is preferable. Arbitrariness.
When other organic polymers are used, the amount thereof used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

  The photosensitive composition of the present invention may further contain a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine and the like in combination.

  A sulfur atom-containing compound is generally used as the chain transfer agent or sensitizer. 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- 3- Mercapto compounds such as mercapto propionates, Disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acids, iodoacetic acids, iodopropionic acids, 2-iodoethanol, 2-iodoethanesulfonic acid, iodos such as 3-iodopropanesulfonic acid Alkylated compounds, 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, diisopropyl thioxanthone, the following compound No. 1 C1, Aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate; Kalens MT BD1, PE1, NR1 manufactured by Showa Denko K. K.

  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 halides and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

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

Examples of the melamine compound, (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, all or part of the (poly) active methylol groups of the nitrogen compound such as methylol urea (CH ₂ OH groups) The compound etc. by which (at least 2) was alkyl-etherified can be mentioned.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group or a butyl group, which may be identical to or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

  The photosensitive composition of the present invention can be a soda glass, quartz glass, semiconductor substrate, metal, paper, plastic by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like. Etc. can be applied on a supporting substrate. In addition, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and the method of application is not limited.

  Moreover, as a light source of energy rays used when curing the photosensitive composition of the present invention, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, Carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. Although an energy ray can be used, preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp and the like which emit light with a wavelength of 300 to 450 nm can be mentioned.

  Furthermore, by using a laser beam as an exposure light source, a laser direct writing method of directly forming an image from digital information of a computer or the like without using a mask improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used, and light with a wavelength of 340 to 430 nm is preferably used as the laser light, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser Also usable are those emitting light in the visible to infrared region such as various semiconductor lasers and YAG lasers. When using these lasers, sensitizing dyes that absorb the relevant region of visible to infrared are added.

  The photosensitive composition of the present invention is a photocurable coating or varnish; a photocurable adhesive; a print substrate; a color filter in a liquid crystal display element for color display such as a color television, a PC monitor, a portable information terminal, a digital camera; Color filter for image sensor, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, gel coat, photoresist for electronics, electroplating resist, etching resist, dry film Solder resists; Resists for producing color filters for various display applications or for forming structures in plasma display panels, electroluminescent displays, and LCD manufacturing processes; compositions for encapsulating electrical and electronic components Solder resists; Magnetic recording materials; Micromachine parts Waveguide, optical switch, mask for plating, etching mask, color test system, glass fiber cable coating, stencil for screen printing, material for producing a three-dimensional object by stereolithography, material for holographic recording, image recording material, Microelectronic circuits; Decolorization materials; Decolorization materials for image recording materials; Decolorization materials for image recording materials using microcapsules; Photoresist materials for printed wiring boards; Photoresist materials for UV and visible laser direct imaging systems; It can be used in various applications such as a photoresist material or a protective film used for forming a dielectric layer in 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 a spacer for a liquid crystal display panel and for the purpose of forming a projection for a vertical alignment type liquid crystal display element. In particular, it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for vertically aligned liquid crystal display devices.

  The above-mentioned spacer for a liquid crystal display panel is (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate, (2) irradiating the coating film with radiation through a mask having a predetermined pattern shape. It is preferably formed by the following steps: (3) baking after exposure, (4) developing the film after exposure, and (5) heating the film after development.

  The (colored) photosensitive composition of the present invention to which an ink repellent agent is added is useful as a partition wall forming resin composition for ink jet system, and the composition is used for a color filter, and in particular, the profile angle is 50 ° or more It is preferably used for certain ink jet system color filter partitions. As the ink repellent agent, a composition comprising a fluorine-based surfactant and a fluorine-based surfactant is suitably used.

  A partition formed of the photosensitive composition according to the present invention divides the surface of the transfer-receiving material, and the optical element is formed by applying droplets to the recessed portion on the divided transfer-receiving material by an inkjet method. Manufactured. At this time, it is preferable that the droplets contain a coloring agent and the image area be colored, and at least a pixel group consisting of a plurality of colored areas and a partition separating the colored areas of the pixel group on the substrate. Preferably, an optical element produced by the method for producing an optical element described above is used.

  The photosensitive composition of the present invention is also used as a composition for a protective film or an insulating film, and is a UV absorber, an alkylated modified melamine and / or an acrylic modified melamine, a monofunctional or bifunctional containing an alcoholic hydroxyl group in the molecule. The (meth) acrylate monomer and / or the silica sol can be contained.

As the photosensitive composition for the said 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 mg KOH / g,
(B) unsaturated compounds containing at least one or more photopolymerizable ethylenic unsaturated bonds in one molecule,
(C) epoxy compound, and (D) photopolymerization initiator,
A resin composition containing
The component (C) is contained in an amount of 10 to 40 parts by weight and the component (D) is contained in an amount of 0.01 to 2.0 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B) What contains the compound represented by the said General formula (I) as a photoinitiator of (component) is preferable.

  The insulating film is used for the insulating resin layer in a laminate in which the insulating resin layer is provided on a peelable support base material, and the laminate is capable of developing with an alkaline aqueous solution, and the insulating resin layer Preferably, the film thickness is 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 barrier rib pattern, a dielectric pattern, an electrode pattern and a black matrix pattern of a plasma display panel.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples and the like.

Example 1 Compound No. 1 54 production
<Step 1> Dissolve 1.14 g (10.0 mmol) of 1-butanone-2-ene, 1- {4- [4- (2-hydroxyethoxy) phenylthio] phenyl} in 200 mL ethanol under a stream of oximation nitrogen; A solution of t-butyl nitrite (50.0 mmol) dissolved in 30 mL of purified water in the presence of hydrochloric acid was added dropwise. 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.
<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 for 2 hours at room temperature, it was washed 3 times with purified water. The organic layer was dried with anhydrous sodium sulfate and desolvated. It refine | purifies using a column, Compound No. which is a target object. Obtained 2.20 g of 54.

Compound No. 54 elemental analysis: (found C: 59.5%, H: 5.9%, N: 5.7%, S: 6.7%, theoretical value C 5 9.00% :, H 5.78%: , N: 5.73%, S: 6.56%)
Mass: 488

[Example 2] Alkali-developable photosensitive resin composition No. 1 Production of <Step 1> Production of Alkali-Developable Resin In a reaction vessel, a bisphenol fluorene type epoxy resin represented by the general formula (VII) ( ^{one in} which X ¹ is represented by (ro), an epoxy equivalent of 231 184 g, acrylic acid 58 g, 0.26 g 2,6-di-tert-butyl-p-cresol, 0.11 g tetra-n-butylammonium bromide and 23 g propylene glycol-1-monomethylether-2-acetate, The mixture was stirred 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 is further added, stirred 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 After adding 90 g of -1-monomethylether-2-acetate, a solution of alkali developable resin No. 1 was obtained as a target propylene glycol-1-monomethylether-2-acetate solution. 1 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mg KOH / g).
<Step 2> Alkali-developable photosensitive resin composition No. 1 Preparation of No. 1 Alkali developable resin No. 1 1 10.7 g, 2.7 g of dipentaerythritol penta and hexaacrylate (ALONIX M-402; made by Toagosei), 1.2 g of a 1% solution of cyclohexanone in surfactant FZ-2122 (made by Nippon Unicar), propylene glycol Compound No. 1 was mixed with 2.7 g of -1-monomethylether-2-acetate and 12.6 g of cyclohexanone. Into the alkali-developable photosensitive resin composition No. 1 of the present invention was added 0.07 g of No. 54, followed by thorough stirring. I got one.
Comparative Example 1 Production of Comparative Alkali-Developable Photosensitive Resin Composition 1 Compound No. 1 of Example 1 <Step 2 of Example 2> except that 54 was replaced by ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) Comparative alkali-developable photosensitive resin composition 1 was obtained in the same manner as in <1>.

<Evaluation of transmittance>
Alkali-developable photosensitive resin composition No. 1 1 and Comparative alkali-developable photosensitive resin composition 1 were evaluated for transmittance as follows.
That is, an alkali-developable photosensitive resin composition was spin-coated (500 rpm, 2 seconds, 800 rpm, 6 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. It was exposed at 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 a spectrophotometer. The results are shown in Table 1.
<Evaluation of sensitivity>
Alkali-developable photosensitive resin composition No. 1 1 and Comparative alkali-developable photosensitive resin composition 1 The sensitivity was evaluated in the following three steps. 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 The case where it was was made into x. The results are shown in Table 1.
<Outgassing>
Alkali-developable photosensitive resin composition No. 1 Outgassing test of the alkali-developable photosensitive resin composition 1 was conducted as follows. That is, a colored alkali-developable photosensitive resin composition is spin-coated (500 rpm, 7 seconds) on a glass substrate, prebaked at 90 ° C. for 90 seconds using a hot plate, and a high pressure mercury lamp as a light source. The exposure was 100 mJ / cm ² . About 3 mg of this film was scraped off, and the outgassing property was evaluated from the weight loss rate when it was kept at 230 ° C. for 30 minutes by TG-DTA (manufactured by Seiko Instruments Inc.). The results are shown in Table 1.

  From the results of Table 1, the alkali-developable photosensitive resin composition No. 1 of the present invention was obtained. It was found that the composition No. 1 exhibited a transmittance higher than that of the comparative alkali-developable photosensitive resin composition 1, had a good sensitivity, and exhibited the effect of reducing the amount of outgassing.

Claims (10)

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

^(Wherein, R 6, ^{R 7} and ^{R 8} each ^{independently} represent a ^{R 11, R 11} represents an alkyl group having carbon atom number of 1 to 20,
The hydrogen atom of the substituent represented by R ¹¹ may be substituted with OR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , CN, a halogen atom, or COOR ²¹ ,
R ^{21, R 22} and ^{R 23} represent a hydrogen ^atom, an alkyl moiety of the substituents represented by ^{R 1 1} is may be the case or cyclic alkyl with branched side chains,
R ⁹ represents a group represented by the following general formula (II-A),
Y represents a vulcanization Kihara child, alpha is to table an integer from 1 to 10. )

(Wherein, ^{Z 3} is a bond, - O - represents,
Z ⁴ is a bond and represents an alkyl group having 1 to 20 carbon atoms substituted with 1 to 3 R ¹⁰ ,
The alkylene moiety of the bond represented by Z ⁴ may be a branched side chain or a cyclic alkylene,
R ¹⁰ represents OR ⁴¹ ,
R ⁴¹ represents a hydrogen atom,
a represents an integer of 1 to 3; )   The oxime ester compound according to claim 1, wherein the α is 1.   Said R ¹¹ The methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl or tert-octyl The oxime ester compound as described in 1 or 2. Said Z ⁴ Is
When a is 1, methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene , 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, nonylene, decylene, dodecylene, tridecylene, tetradecylene, pentadecylene, ethane-1, 1-diyl or propane-2,2-diyl;
When a is 2, any one of these groups is one R ¹⁰ A group substituted by
When a is 3, any one of these groups is two R ¹⁰ The oxime ester compound according to any one of claims 1 to 3, which is a group substituted by The photoinitiator containing the oxime ester compound as described in any one of Claims 1-4. A photosensitive composition comprising the photopolymerization initiator according to claim 5 and a polymerizable compound. The photosensitive composition whose polymeric compound of Claim 6 is a polymeric compound which has an ethylenically unsaturated bond. The alkali developable photosensitive resin composition which makes the photosensitive composition as described in any one of Claims 6 and 7 contain the polymeric compound which has group which gives alkali developability. A colored alkali-developable photosensitive resin composition, which further comprises a coloring material in the alkali-developable photosensitive resin composition according to claim 8 . The photosensitive composition according to any one of claims 6 and 7 , the alkali-developable photosensitive resin composition according to claim 8 , or the colored alkali-developable photosensitive resin composition according to claim 9 Cured product irradiated with energy rays.