JP6936215B2 - Photopolymerization initiator composition and photosensitive composition - Google Patents

Description

The present invention comprises a photopolymerization initiator composition useful as a photopolymerization initiator component used in a photosensitive composition, and a polymerizable compound having an ethylenically unsaturated bond in the photopolymerization initiator composition. With respect to the photosensitive composition.

The photosensitive composition is a polymerizable compound having an ethylenically unsaturated bond to which a photopolymerization initiator is added, and since it can be irradiated with energy rays (light), it is a photocurable ink and a photosensitive printing plate. , Used in various photoresists and the like.

As the photopolymerization initiator used in the photosensitive composition, Patent Documents 1 to 7 below propose the use of an oxime ester compound.
However, each of these conventional photopolymerization initiators has insufficient sensitivity, and when used in an alkali-developable photosensitive resin composition or the like, the resolution is not sufficiently satisfactory.

U.S. Patent Application Publication No. 2004/170924 U.S. Patent Application Publication No. 2007/270522 U.S. Patent Application Publication No. 2009/292039 U.S. Patent Application Publication No. 2011/129778 EP2407456A1 EP2433927A1 Special Table 2013-543875

Therefore, an object of the present invention is to provide a photopolymerization initiator composition capable of imparting excellent sensitivity and resolution to a photosensitive composition, and a photosensitive composition using the photopolymerization initiator composition. It is in.

As a result of diligent studies to solve the above problems, the present inventors have excellent sensitivity and resolution by using an oxime ester compound having a specific ether structure and an oxime ester compound having a specific cycloalkyl structure in combination. Was found to be a photopolymerization initiator composition that can be imparted to a photosensitive composition, and the present invention has been completed.

That is, the present invention contains 1 to 99 parts by mass of the following component (A) and 1 to 99 parts by mass of the following component (B) (however, the total of the components (A) and (B) is 100 parts by mass). It provides a polymerization initiator composition.

Component (A): Contains one or more of the oxime ester compounds represented by the following general formulas (1-1) to (1-3), which have an ether structure represented by the following general formula (3). Photopolymerization initiator.

一般式（１−１）〜（１−３）中、Ｒ¹、Ｒ²及びＲ⁶は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜３０のアリール基、炭素原子数６〜３０のアリールオキシ基、炭素原子数７〜３０のアラルキル基、炭素原子数２〜２０の複素環基又はシアノ基を表し、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アラルキル基及び複素環基の水素原子は、更にＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＮＲ¹²Ｒ¹³、−ＮＣＯＲ¹²−ＯＣＯＲ¹³、ＣＮ、ハロゲン原子、−ＣＲ¹¹＝ＣＲ¹²Ｒ¹³又は−ＣＯ−ＣＲ¹¹＝ＣＲ¹²Ｒ¹³で置換されている場合があり、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のアラルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ¹、Ｒ²、Ｒ⁶、Ｒ¹¹、Ｒ¹²及びＲ¹³で表される置換基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されている場合があり、上記置換基のアルキル部分は分岐側鎖がある場合があり、環状アルキルである場合があり、上記置換基のアルキル末端は不飽和結合である場合があり、Ｒ²は、隣接するベンゼン環と一緒になって環を形成している場合がある。
Ｒ³、Ｒ⁴及びＲ⁵は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜３０のアリール基、炭素原子数６〜３０のアリールオキシ基、炭素原子数７〜３０のアラルキル基、炭素原子数２〜２０の複素環基、シアノ基又はハロゲン原子を表し、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アラルキル基及び複素環基の水素原子は、更にＯＲ¹⁴、ＣＯＲ¹⁴、ＳＲ¹⁴、ＮＲ¹⁵Ｒ¹⁶、−ＮＣＯＲ¹⁵−ＯＣＯＲ¹⁶、ＣＮ、ハロゲン原子、−ＣＲ¹⁴＝ＣＲ¹⁵Ｒ¹⁶又は−ＣＯ−ＣＲ¹⁴＝ＣＲ¹⁵Ｒ¹⁶で置換されている場合があり、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶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のアラルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶で表される置換基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されている場合があり、上記置換基のアルキル部分は分岐側鎖がある場合があり、環状アルキルである場合があり、上記置換基のアルキル末端は不飽和結合である場合があり、ａ、ｂ及びｄは、それぞれ独立に、０〜３の整数である。
Ａ¹は、上記一般式（３）で表され、一般式（３）中、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ独立に、水素原子又は炭素原子数１〜２０のアルキル基を表し、アルキル基の水素原子はハロゲン原子で置換されている場合があり、アルキル基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されている場合があり、アルキル部分は分岐側鎖がある場合があり、環状アルキルである場合があり、アルキル末端は不飽和結合である場合があり、Ｒ⁷とＲ⁸は、一緒になって環を形成している場合がある。

In the general formulas (1-1) to (1-3), R ¹ , R ² and R ⁶ are independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and carbon. Represents an aryl group having 6 to 30 atoms, an aryloxy group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group or a cyano group having 2 to 20 carbon atoms, and an alkyl group or an alkoxy group. The hydrogen atoms of the group, aryl group, aryloxy group, aralkyl group and heterocyclic group are further OR ¹¹ , COR ¹¹ , SR ¹¹ , NR ¹² R ¹³ , -NCOR ^{12- OCOR 13} , CN, halogen atom, -CR ¹¹ = CR ¹² R ¹³ or -CO-CR ¹¹ = CR ¹² R ¹³ may be substituted, and R ¹¹ , R ¹² and R ¹³ are independently alkyl hydrogen atoms and 1 to 20 carbon atoms, respectively. Represents a group, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and represents R ¹ , R ² , R ⁶ , R ¹¹ , R ^{12 above.} And ^{the alkylene moiety of the substituent represented by R 13} may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl moiety of the group may have a branched side chain, it may be cyclic alkyl, the alkyl end of the substituent may be an unsaturated bond, and R ² is combined with the adjacent benzene ring. May form a ring.
R ³ , R ⁴ and R ⁵ independently have an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 6 to 30 carbon atoms. Represents an aryloxy group, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and The hydrogen atoms of the heterocyclic group are further OR ¹⁴ , COR ¹⁴ , SR ¹⁴ , NR ¹⁵ R ¹⁶ , -NCOR ¹⁵ -OCOR ¹⁶ , CN, halogen atom, -CR ¹⁴ = CR ¹⁵ R ¹⁶ or -CO-CR ¹⁴ = CR ¹⁵ R ¹⁶ may be substituted, and R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms, respectively. It represents an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and is an alkylene moiety of a substituent represented by ^{R 3} , R ⁴ , R ⁵ , R ¹⁴ , R ¹⁵ and R ^{16 above.} May be interrupted 1 to 5 times by unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane bond, and the alkyl moiety of the above substituent may have a branched side chain. Yes, it may be cyclic alkyl, the alkyl end of the substituent may be an unsaturated bond, and a, b and d are independently integers from 0 to 3.
A ¹ is represented by the above general formula (3), and in the general formula (3), R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The hydrogen atom of the alkyl group may be substituted with a halogen atom, and the methylene group of the alkylene portion of the alkyl group is 1 due to an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. It may be interrupted ~ 5 times, the alkyl moiety may have a branched side chain, it may be cyclic alkyl, the alkyl terminal may be unsaturated, and R ⁷ and R ⁸ may be They may form a ring together.

Component (B): Light containing one or more of the oxime ester compounds represented by the following general formula (2-1) or (2-2), which has the cycloalkyl structure of the following general formula (4). Polymerization initiator.

一般式（２−１）又は（２−２）中、Ｒ²¹及びＲ²²は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜３０のアリール基、炭素原子数６〜３０のアリールオキシ基、炭素原子数７〜３０のアラルキル基、炭素原子数２〜２０の複素環基又はシアノ基を表し、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アラルキル基及び複素環基の水素原子は、更にＯＲ³¹、ＣＯＲ³¹、ＳＲ³¹、ＮＲ³²Ｒ³³、−ＮＣＯＲ³²−ＯＣＯＲ³³、ＣＮ、ハロゲン原子、−ＣＲ³¹＝ＣＲ³²Ｒ³³又は−ＣＯ−ＣＲ³¹＝ＣＲ³²Ｒ³³で置換されている場合があり、Ｒ³¹、Ｒ³²及びＲ³³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のアラルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ²¹、Ｒ²²、Ｒ³¹、Ｒ³²及びＲ³³で表される置換基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されている場合があり、上記置換基のアルキル部分は分岐側鎖がある場合があり、環状アルキルである場合があり、上記置換基のアルキル末端は不飽和結合である場合があり、Ｒ²²は、隣接するベンゼン環と一緒になって環を形成している場合がある。
Ｒ²³及びＲ²⁴は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜３０のアリール基、炭素原子数６〜３０のアリールオキシ基、炭素原子数７〜３０のアラルキル基、炭素原子数２〜２０の複素環基、シアノ基又はハロゲン原子を表し、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アラルキル基及び複素環基の水素原子は、更にＯＲ³⁴、ＣＯＲ³⁴、ＳＲ³⁴、ＮＲ³⁵Ｒ³⁶、−ＮＣＯＲ³⁵−ＯＣＯＲ³⁶、ＣＮ、ハロゲン原子、−ＣＲ³⁴＝ＣＲ³⁵Ｒ³⁶又は−ＣＯ−ＣＲ³⁴＝ＣＲ³⁵Ｒ³⁶で置換されている場合があり、Ｒ³⁴、Ｒ³⁵及びＲ³⁶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のアラルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ²³、Ｒ²⁴、Ｒ³⁴、Ｒ³⁵及びＲ³⁶で表される置換基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されている場合があり、上記置換基のアルキル部分は分岐側鎖がある場合があり、環状アルキルである場合があり、上記置換基のアルキル末端は不飽和結合である場合があり、ｕ及びｖは、それぞれ独立に、０〜３の整数である。
Ａｒは下記の構造から選ばれるアリール基又は複素環基を表し、

Ｌ¹は、水素原子又はベンゾイル基を表し、
Ｘ¹は、直接結合又はカルボニル基を表し、
Ｇ¹は、一般式（４）の基を表し、一般式（４）中、ｎは１〜５の整数であり、ｍは１〜６の整数である。

In the general formula (2-1) or (2-2), R ²¹ and R ²² independently have an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 carbon atoms, respectively. Represents an aryl group of ~ 30, an aryloxy group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group or a cyano group having 2 to 20 carbon atoms, and an alkyl group, an alkoxy group, or an aryl group. The hydrogen atoms of the group, aryloxy group, aralkyl group and heterocyclic group are further OR ³¹ , COR ³¹ , SR ³¹ , NR ³² R ³³ , -NCOR ³² -OCOR ³³ , CN, halogen atom, -CR ³¹ = CR ^32. R ³³ or -CO-CR ³¹ = CR ³² R ³³ may be substituted, and R ³¹ , R ³² and R ³³ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and carbons. It represents an aryl group having 6 to 30 atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and is represented by R ²¹ , R ²² , R ³¹ , R ³² and R ^33. The alkylene moiety of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl moiety of the above substituent is branched. There may be a side chain, it may be cyclic alkyl, the alkyl end of the substituent may be an unsaturated bond, and R ²² forms a ring with the adjacent benzene ring. May be present.
R ²³ and R ²⁴ independently have an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aryloxy having 6 to 30 carbon atoms. Represents a group, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and a heterocyclic group. The hydrogen atoms of are further OR ³⁴ , COR ³⁴ , SR ³⁴ , NR ³⁵ R ³⁶ , -NCOR ^{35- OCOR 36} , CN, halogen atom, -CR ³⁴ = CR ³⁵ R ³⁶ or -CO-CR ³⁴ = CR ³⁵ R. It may be substituted with ^{36 , and R 34} , R ³⁵ and R ³⁶ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and carbon atoms, respectively. The alkylene moiety of the substituent representing 7 to 30 aralkyl groups or heterocyclic groups having 2 to 20 carbon atoms and represented by R ²³ , R ²⁴ , R ³⁴ , R ³⁵ and R ^{36 is an unsaturated bond.} It may be interrupted 1 to 5 times by an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl moiety of the above substituent may have a branched side chain and is cyclic alkyl. In some cases, the alkyl end of the substituent may be an unsaturated bond, where u and v are independently integers from 0 to 3.
Ar represents an aryl group or a heterocyclic group selected from the following structures.

L ¹ represents a hydrogen atom or a benzoyl group
X ¹ represents a direct bond or carbonyl group
G ¹ represents the group of the general formula (4), in which n is an integer of 1 to 5 and m is an integer of 1 to 6.

The present invention also provides a photosensitive composition obtained by incorporating the above-mentioned photopolymerization initiator composition into a polymerizable compound having an ethylenically unsaturated bond.
The present invention also provides the above-mentioned photosensitive composition further containing an inorganic compound.

Further, in the present invention, the photopolymerization initiator composition is contained in an alkali-developable compound which may have an ethylenically unsaturated bond and a polymerizable compound which has an ethylenically unsaturated bond. It provides a photosensitive tree composition.
The present invention also provides the alkali-developable photosensitive resin composition further containing an inorganic compound.

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.
The present invention also provides a cured product obtained by irradiating the photosensitive composition, the alkali-developable photosensitive composition or the colored alkali-developable photosensitive resin composition with energy rays.

The photopolymerization initiator composition of the present invention will be described.

The oxime ester compound used as the component (A) in the photopolymerization initiator composition of the present invention is represented by the above general formulas (1-1) to (1-3) and is represented by the above general formula (3). It is characterized by having an ether structure.

The oxime ester compound used as the component (A) has geometric isomers due to double bonds of oxime, but these are not distinguished, and the above general formulas (1-1) to (1-3) and the following will be described. The example compound of is represented by a mixture of both or one of them, and is not limited to a structure showing an isomer.

In addition, the component (A) in the present invention contains one or more of the oxime ester compounds represented by the above general formulas (1-1) to (1-3), and only one or more of the oxime ester compounds. It is preferably composed of.

^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R in the above general formulas (1-1) to (1-3). ^{Examples of the alkyl group having 1 to 20 carbon atoms represented by 16} include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, and heptyl. , Octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.

The alkoxy group having 1 to 20 carbon atoms represented by ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formulas (1-1) to (1-3) is described above. Those corresponding to the alkyl group can be mentioned.

^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R in the above general formulas (1-1) to (1-3). ^{Examples of the aryl group having 6 to 30 carbon atoms represented by 16} include phenyl, tolyl, xsilyl, ethylphenyl, chlorophenyl, biphenylyl, naphthyl, anthryl, phenanthrenyl, and phenyl and biphenylyl substituted with one or more of the above alkyl groups. , Naftil, Anthrill and the like.

As the aryloxy group having 6 to 30 carbon atoms represented by ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formulas (1-1) to (1-3), Those corresponding to the above aryl group can be mentioned.

^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R in the above general formulas (1-1) to (1-3). ^{Examples of the aralkyl group having 7 to 30 carbon atoms represented by 16} include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R in the above general formulas (1-1) to (1-3). ^{Examples of the heterocyclic group having 2 to 20 carbon atoms represented by 16} include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolydyl, and the like. Examples thereof include 5- to 7-membered heterocycles such as thiazolidyl, isothiazolydyl, oxazolidyl, isooxazolydyl, piperidyl, piperazyl and morpholinyl.

An alkyl group having 1 to 20 carbon atoms represented by ^{R 7} , R ⁸ , and R ⁹ in the general formula (3), which represents ^{A 1} in the general formulas (1-1) to (1-3). Examples thereof include the above-mentioned alkyl group.

^{Among the oxime ester compounds of the component (A), those in which R 1} is an alkyl group having 1 to 20 carbon atoms in the above general formulas (1-1) to (1-3) from the viewpoint of sensitivity and resolution. Is preferable, those having an alkyl group having 1 to 4 carbon atoms are more preferable, and a methyl group is even more preferable.

Further, in the above general formulas (1-1) and (1-2), from the viewpoint of sensitivity and resolution, ^{it is preferable that R 2} is an alkyl group having 1 to 20 carbon atoms, and the carbon atoms are 1 to 8. Alkyl groups are more preferred, and ethyl groups are even more preferred.

^{Further, in (R 3} ) a of the above general formulas (1-1) to (1-3), a is preferably 0 or 1, more preferably 0, from the viewpoint of sensitivity and resolution. When a is 1 to 3, R ³ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

^{Further, in (R 4} ) b of the above general formulas (1-1) to (1-3), b is preferably 0 or 1, more preferably 0, from the viewpoint of sensitivity and resolution. When b is 1 to 3, R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

^{Further, in (R 5} ) d of the above general formulas (1-1) to (1-3), d is preferably 0 or 1 and more preferably 1 from the viewpoint of sensitivity and resolution. When d is 1 to 3, R ⁵ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

Further, in the above general formulas (1-1) and (1-3), from the viewpoint of sensitivity and resolution, R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Is more preferable, and a methyl group is even more preferable.

The oxime ester compound of the component (A) is characterized by having an ether structure of ^{A 1 represented by the above general formula (3).} As a result, it has excellent sensitivity and resolution when used in combination with component (B).

In the above general formula (3), from the viewpoint of sensitivity and resolution, R ⁹ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and hydrogen. Atoms or methyl groups are even more preferred.

Further, from the viewpoint of sensitivity and resolution, R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, from the viewpoint of sensitivity and resolution, R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, ^{it is preferable that R 7} and R ⁸ form a ring together, and it is also preferable that R 7 and R 8 have an ether bond in the ring. A preferred specific example of a ring formed by R ⁷ and R ^{8 together is a dimethyldioxolane ring.}

As a preferable specific example of the oxime ester compound represented by the above general formula (1-1) of the component (A), the following compound No. 1 to 4 can be mentioned.

As a preferable specific example of the oxime ester compound represented by the above general formula (1-2) of the component (A), the following compound No. 5-No. 8 is mentioned.

As a preferable specific example of the oxime ester compound represented by the above general formula (1-3) of the component (A), the following compound No. 9 to No. 12 can be mentioned.

Next, the component (B) will be described.
The oxime ester compound used as the component (B) in the photopolymerization initiator composition of the present invention is represented by the above general formula (2-1) or (2-2), and is represented by the above general formula (4). It is characterized by having a cycloalkyl structure.

The oxime ester compound used as the component (B) has geometric isomers due to a double bond of oxime, but these are not distinguished, and the above general formula (2-1) or (2-2) and the following will be described. The example compound of is represented by a mixture of both or one of them, and is not limited to a structure showing an isomer.

In addition, the component (B) in the present invention contains one or more of the oxime ester compounds represented by the above general formula (2-1) or (2-2), and only one or more of the oxime ester compounds. It is preferably composed of.

Carbon represented by ^{R 21} , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the above general formula (2-1) or (2-2). Examples of the alkyl group having 1 to 20 atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2 -Ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like can be mentioned.

The alkoxy group having 1 to 20 carbon atoms represented by ^{R 21} , R ²² , R ²³ , and R ²⁴ in the general formula (2-1) or (2-2) corresponds to the above alkyl group. Things can be mentioned.

Carbon represented by ^{R 21} , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the above general formula (2-1) or (2-2). Examples of the aryl group having 6 to 30 atoms include phenyl, trill, xsilyl, ethylphenyl, chlorophenyl, biphenylyl, naphthyl, anthryl, phenanthrenyl, and phenyl, biphenylyl, naphthyl and anthryl substituted with one or more of the above alkyl groups. Can be mentioned.

The aryloxy group having 6 to 30 carbon atoms represented by ^{R 21} , R ²² , R ²³ and R ²⁴ in the general formula (2-1) or (2-2) corresponds to the above aryl group. Things can be mentioned.

Carbon represented by ^{R 21} , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the above general formula (2-1) or (2-2). Examples of the aralkyl group having 7 to 30 atoms include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

Carbon represented by ^{R 21} , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the above general formula (2-1) or (2-2). Examples of the heterocyclic group having 2 to 20 atoms include pyridyl, pyrimidyl, frill, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolydyl, thiazolidyl, isothiazolydyl, oxazolidyl, and the like. Examples thereof include 5- to 7-membered heterocycles such as isooxazolidyl, piperidyl, piperazyl and morpholinyl.

Among the oxime ester compounds of the component (B), in the above general formula (2-1) or (2-2), from the viewpoint of sensitivity and resolution, R ²¹ is an alkyl group or a carbon atom having 1 to 20 carbon atoms. An aryl group having a number of 6 to 30 is preferable, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms is more preferable, and a methyl group or a phenyl group is even more preferable.

Further, in the above general formula (2-1), from the viewpoint of sensitivity and resolution, ^{it is preferable that R 22} is an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 8 carbon atoms is preferable. More preferably, an ethyl group is even more preferable.

^{Further, in (R 23} ) u of the above general formula (2-1) or (2-2), u is preferably 0 or 1, more preferably 0, from the viewpoint of sensitivity and resolution. When u is 1 to 3, R ²³ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

^{Further, in (R 24} ) v of the above general formula (2-1) or (2-2), v is preferably 0 or 1, more preferably 0, from the viewpoint of sensitivity and resolution. When v is 1 to 3, R ²⁴ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

Further, in the above general formula (2-1), X ¹ is preferably directly coupled from the viewpoint of sensitivity and resolution.

Further, in the above general formula (2-1), Ar is preferably an aryl group or a heterocyclic group selected from the following structures from the viewpoint of sensitivity and resolution.

The oxime ester compound of the component (B) is characterized by having ^{a G 1 cycloalkyl structure represented by the above general formula (4).} As a result, it has excellent sensitivity and resolution when used in combination with the component (A).

In the above general formula (4), n is preferably 1 or 2 from the viewpoint of sensitivity and resolution.

In the above general formula (4), m is preferably 3 or 4 from the viewpoint of sensitivity and resolution. In this case, it has a cyclopentane ring and a cyclohexane ring, respectively.

As a preferable specific example of the oxime ester compound represented by the general formula (2-1) of the component (B), the following compound No. 13-No. 20 is mentioned.

As a preferable specific example of the oxime ester compound represented by the general formula (2-2) of the component (B), the following compound No. 21-No. 26 is mentioned.

In the photopolymerization initiator composition of the present invention, the total content of the component (A) and the component (B) is 100 parts by mass, and the content of the component (A) is 1 part by mass to 99 parts by mass. B) The content of the component is 1 to 99 parts by mass. From the viewpoint of sensitivity and resolution, the content of the component (A) is preferably 20 to 80 parts by mass, more preferably 40 to 60 parts by mass, and the content of the component (B) is preferably 20 to 80 parts by mass, and 40 to 40 parts by mass. 60 parts by mass is more preferable.

In addition to the components (A) and (B), the photopolymerization initiator composition of the present invention has other photopolymerization initiators, for example, Irgacure 369 (manufactured by BASF) and Irgacure 907 (manufactured by BASF). , Irgacure OXE-01 (manufactured by BASF), Irgacure OXE-02 (manufactured by BASF), Lucillin TPO (manufactured by BASF), Irgacure 819 (manufactured by BASF), 2,2-bis (2-chlorophenyl)- It can contain 4,5,4', 5'-tetraphenyl-1-2'-biimidazole and the like. As for the details of these optional components, the description of these components in the photosensitive composition of the present invention described later can be appropriately applied.

Next, the photosensitive composition of the present invention will be described.
The photosensitive composition of the present invention contains the photopolymerization initiator composition of the present invention and a polymerizable compound having an ethylenically unsaturated bond as essential components, and contains optional components such as an inorganic compound, a coloring material, and a solvent. To do.

The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in a photosensitive composition can be used. For example, ethylene, propylene, butylene, isobutylene and vinyl chloride can be used. , Vinylidene chloride, vinylidene fluoride, tetrafluoroethylene and other unsaturated aliphatic hydrocarbons; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, Isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinate [2- (meth) acrylicyloxyethyl], monophthalate [2- (meth) acrylicyloxyethyl], ω- Mono (meth) acrylate of a polymer having carboxy groups and hydroxyl groups at both ends, such as carboxypolycaprolactone mono (meth) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene. Unsaturated polybasic acids such as malate or polyfunctional (meth) acrylates with one carboxyl group and two or more (meth) acryloyl groups; -2-hydroxyethyl (meth) acrylic acid, (meth) acrylic acid -2-Hydroxypropyl, glycidyl (meth) acrylate, the following compound No. A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, Aminopropyl (Meta) Acrylate, Dimethylaminopropyl (Meta) Acrylate, ethoxyethyl (Meta) Acrylate, Poly (ethoxy) Ethyl (Meta) Acrylate, Butoxyethoxyethyl (Meta) Acrylate, (Meta) ) Ethylhexyl acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanthry (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, Unsaturated monobasic acids such as pentaerythritol tri (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomer, and polyhydric alcohols or polyvalents. Esters of phenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate, magnesium (meth) acrylate; maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, methyltetrahydrophthalic anhydride, tetrahydro Acrylate, TrialkyltetrahydroAcrylate, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthaliclate-anhydrous Acid anhydrides of unsaturated polybasic acids such as maleic acid adduct, dodecenyl anhydride succinic acid, methylhymic anhydride; (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) Amid of unsaturated monobasic acids and polyvalent amines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as achlorine; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol , Vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether and other unsaturated aromatic compounds; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidin and the like. Unsaturated amine compounds; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; maleimide, N-phenylmaleimide, N-cyclohexyl Unsaturated imides such as maleimide; indens such as inden and 1-methylinden; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n-butyl ( Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains such as meta) acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isothia Examples thereof include nurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, a vinylurethane compound of a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, and a vinyl epoxy compound of a hydroxyl group-containing vinyl monomer and a polyepoxy compound.

Among these, mono (meth) acrylates of polymers having carboxy groups and hydroxyl groups at both ends, polyfunctional (meth) acrylates having one carboxy group and two or more (meth) acryloyl groups, unsaturated ones. The photopolymerization initiator composition of the present invention is suitable for esters of basic acids and polyhydric alcohols or polyhydric phenols.

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. You can also do it.

Further, the photosensitive composition of the present invention may be made into an alkali-developable photosensitive resin composition by using an alkali-developable compound having an ethylenically unsaturated bond as the polymerizable compound having an ethylenically unsaturated bond. can. Examples of the alkali-developable compound having an ethylenically unsaturated bond include a copolymer of an acrylic acid ester, a phenol and / or cresol novolac epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy acrylate resin. 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 (5) and further allowing a polybasic acid anhydride to act 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 (5) and further allowing a polybasic acid anhydride to act is preferable.

Further, the alkali developable compound having an ethylenically unsaturated bond preferably contains an unsaturated group in an amount of 0.2 to 1.0 equivalent.

（一般式（５）中、Ｘ²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又は下記一般式（６）、式（７）若しくは一般式（８）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ている場合があり、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³及びＲ⁴⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されている場合があり、ｔは０〜１０の整数であり、ｔが０でないときに存在する光学異性体は、どの異性体でもよい。）

(In the general formula (5), X ² 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, Represents SO, CO, OCO or a substituent represented by the following general formula (6), formula (7) or general formula (8), and the alkylidene group may be substituted with a halogen atom, R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ independently have 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. The above alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, t is an integer of 0 to 10, and the optical isomer present when t is not 0 can be any isomer. good.)

（一般式（６）中、Ｚ¹は水素原子、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されている場合があるフェニル基、又は炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されている場合がある炭素原子数３〜１０のシクロアルキル基を示し、Ｙ¹は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を示し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されている場合があり、ｗは０〜５の整数である。）

(In the general formula (6), Z ¹ may be substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, or a phenyl group having 1 to 10 carbon atoms. Indicates a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group of 10 or an alkoxy group having 1 to 10 carbon atoms, and Y ¹ is an alkyl group having 1 to 10 carbon atoms or a carbon atom. It represents an alkoxy group having the number 1 to 10 and an alkenyl group or a halogen atom having 2 to 10 carbon atoms, and the alkyl group, the alkoxy group and the alkenyl group may be substituted with a halogen atom, and w is 0 to 5. It is an integer.)

（一般式（８）中、Ｙ²及びＺ²は、それぞれ独立して、ハロゲン原子で置換されている場合がある炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されている場合がある炭素原子数６〜２０のアリール基、ハロゲン原子で置換されている場合がある炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換されている場合がある炭素原子数６〜２０のアリールチオ基、ハロゲン原子で置換されている場合がある炭素原子数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る場合がある炭素原子数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る場合がある炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されている場合があり、Ｚ²は、隣接するＺ²同士で環を形成している場合があり、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。）

(In the general formula (8), Y ² and Z ² may be independently substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom, respectively. Aryl groups with 6 to 20 carbon atoms, aryloxy groups with 6 to 20 carbon atoms that may be substituted with halogen atoms, arylthio groups with 6 to 20 carbon atoms that may be substituted with halogen atoms. , Arylalkenyl groups with 6 to 20 carbon atoms that may be substituted with halogen atoms, arylalkyl groups with 7 to 20 carbon atoms that may be substituted with halogen atoms, and halogen atoms. In some cases, it represents a heterocyclic group having 2 to 20 carbon atoms or a halogen atom, and the alkylene moiety in the above-mentioned alkyl group and arylalkyl group is interrupted by an unsaturated bond, -O- or -S-. There are, Z ² is may form a ring with the adjacent Z ² together, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r is 0 to 4 integer , S represents an integer of 0-4, and the sum of the numbers of r and s is an integer of 2-4.)

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, and hydroxypropyl. Examples thereof include acrylate malate and dicyclopentadiene malate.

Further, as the polybasic acid anhydride to be actuated after the unsaturated monobasic acid is allowed to act, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, and the like. Trimellitic hydride, pyromellitic hydride, 2,2'-3,3'-benzophenone tetracarboxylic hydride, ethylene glycol bisamhydrotrimeritate, glycerol trisanhydrotrimeritate, hexahydrophthalic anhydride , Methyltetrahydrohydride phthalic acid, Nagicic acid anhydride, Methylnadic acid anhydride, Trialkyltetrahydroanhydride, Hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydride succinic acid, methyl hymic anhydride and the like can be mentioned.

The reaction molar ratios of the epoxy compound, the unsaturated monobasic acid and the polybasic anhydride are preferably as follows.
That is, in an 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 1 of the epoxy adduct It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 with respect to the number of the polybasic acid anhydride.

The reaction of the epoxy compound, the unsaturated monobasic acid and the 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, has an ethylenically unsaturated bond with the photopolymerization initiator composition of the present invention as an essential component. It contains a polymerizable compound having an ethylenically unsaturated bond and an alkali-developable compound which may have an ethylenically unsaturated bond, and contains a combination of components such as an inorganic compound, a coloring material, and a solvent as optional components. .. 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 composition of the present invention.

The above-mentioned polymerizable compound having an ethylenically unsaturated bond and the above-mentioned alkali-developable compound which may have an ethylenically unsaturated bond may be the same compound or may be different. In addition, it may be used alone or in combination of two or more.

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

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, and heptyl. Glycyzyl 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 monooxide, 1,2-epoxy- 4-Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compound No. E1, No. E2 and the like can be mentioned.

When one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers are used as the polyfunctional epoxy compound, a (colored) alkali-developable photosensitive resin composition having even better characteristics can be obtained. It is preferable because it can be used.

As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (5) 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, and 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 di Diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri ( Diglycidyl oxymethyl) methane, 1,1,1,1-tetra (glycidyl oxymethyl) methane and the like can be used.

In addition, novolak type epoxy compounds such as phenol novolac type epoxy compound, biphenyl novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound; 3,4-epoxy-6-methyl Alicyclic epoxys such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compounds; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene A type epoxy compound or the like can also be used.

In the photosensitive composition of the present invention, in the photopolymerization initiator composition of the present invention, a photopolymerization initiator composition is prepared in advance from the components (A) and (B), and the photopolymerization initiator composition is ethylenically unsaturated. It can be blended with a polymerizable compound having a bond or other optional component, and the component (A) and the component (B) can be separately blended with the polymerizable compound or other optional component to obtain a photosensitive composition. You can also do it.

In the photosensitive composition of the present invention, the content of the photopolymerization initiator composition of the present invention is not particularly limited, but the polymerizable compound having the ethylenically unsaturated bond (or the ethylenically unsaturated bond) is not particularly limited. The amount is preferably 0.1 to 70 parts by mass, more preferably 0.3 to 50 parts by mass, and most preferably 0.5 to 30 parts by mass with respect to 100 parts by mass.

In particular, when the photosensitive composition of the present invention is a (colored) alkali-developable photosensitive resin composition, the content of the photopolymerization initiator composition of the present invention is the (colored) alkali-developable photosensitive of the present invention. Of the solid content (all components other than the solvent) of the resin composition, 0.3 to 20% by mass, particularly 0.8 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 components (the photopolymerization initiator composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond, etc.) as required, for example, methyl ethyl ketone. Ketones such as methylamyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, di Ether solvents such as propylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, -n-propyl acetate, 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 acetate, ethylene glycol monoethyl acetate, propylene Ether ester solvents such as glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene; hexane, heptane , Octane, cyclohexane and other aliphatic hydrocarbon solvents; terpine oil, D-lymonen, pinen and other terpenic hydrocarbon oils; Mineral Spirit, Swazole # 310 (Cosmo Matsuyama Petroleum Co., Ltd.), Solbesso # 100 (Exxon Chemical) Paraffin-based solvent such as ()); Halogened aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogenized aromatic hydrocarbon solvent such as chlorobenzene; Calvi Thor-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide; water and the like. It can be used as one kind or a mixed solvent of two or more kinds.

Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are preferable because they have good compatibility between the resist and the photopolymerization initiator in the photosensitive composition.
When a solvent is used in the photosensitive composition of the present invention, the amount used is preferably an amount in which the concentration of the solid content (components other than the solvent) is 5 to 85% by mass from the viewpoint of handling and the like.

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

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

As the above pigment, a commercially available pigment can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet Examples thereof include 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50.

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

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 and calcium carbonate. Magnesium carbonate, cobalt-based, manganese-based, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfide, serene, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Examples include gold, silver and copper. 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. It is 800 parts by mass. In addition, one kind or two or more kinds of these inorganic compounds can be used.
These inorganic compounds are used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents and the like.

A dispersant that disperses a coloring material and / or an inorganic compound can be added to the photosensitive composition of the present invention. The dispersant is not limited as long as it can disperse and stabilize the coloring material or the inorganic compound, and a commercially available dispersant, for example, the BYK series manufactured by Big Chemie, etc. can be used. In particular, a polymer dispersant made of polyester, polyether, or polyurethane having a basic functional group, a functional group having a nitrogen atom as a basic functional group and having a nitrogen atom is an amine and / or a quaternary salt thereof. , Amine with an amine value of 1 to 100 mgKOH / g is preferably used.

In the photosensitive composition of the present invention, another photopolymerization initiator can be used in combination with the oxime ester compound of the component (A) and the oxime ester compound of the component (B). 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, benzyldimethylketal, 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-benzoyl propane, 2-hydroxy-2- (4'-isopropyl) benzoyl propane, 4-butyl benzoyl trichloromethane, 4-phenoxy Benzoyl dichloromethane, methyl benzoyl formate, 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, Examples thereof include N-1717 (manufactured by ADEKA Co., Ltd.), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Japan Co., Ltd.), benzoyl peroxide, and compounds represented by the following general formula (9). When these other photopolymerization initiators are used, the amount used is preferably 1% by mass or less of the total amount of the components (A) and (B) used in the photopolymerization initiator composition of the present invention. do. In addition, these photopolymerization initiators can be used alone or in combination of two or more.

（一般式（９）中、Ｒ¹、Ｒ²及びＲ⁶は、上記一般式（１−２）と同じであり、Ｒ⁵¹はハロゲン原子又はアルキル基を表し、ｅは０〜５の整数である。）

(In the general formula (9), R ¹ , R ² and R ⁶ are the same as the above general formula (1-2), R ⁵¹ represents a halogen atom or an alkyl group, and e is an integer of 0 to 5. be.)

Further, in the photosensitive composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizer; adhesion accelerator; filler; defoamer. Conventional additives such as foaming agents; leveling agents; surface conditioners; antioxidants; ultraviolet absorbers; dispersion aids; anti-aggregation agents; catalysts; effect promoters; cross-linking agents; thickeners can be added.

In the photosensitive composition of the present invention, any component other than the polymerizable compound having an ethylenically unsaturated bond and the photopolymerization initiator composition of the present invention (provided that the other photopolymerization initiator described above is ethylenically unsaturated). The amount of the alkali-developable compound, the inorganic compound (filler), the coloring material, and the solvent, which may have a group, is appropriately selected according to the purpose of use and is not particularly limited, but is preferable. Is 50 parts by mass or less in total with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

Further, the properties of the cured product can be improved by using another organic polymer together with the above-mentioned polymerizable compound having an ethylenically unsaturated bond in the photosensitive composition of the present invention. Examples of the organic polymer include polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmethacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples thereof include polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Among these, polystyrene, (meth) acrylic acid-methylmethacrylate copolymer, and epoxy resin are preferable.
When another organic polymer is used, the amount 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.

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

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thioapple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-[N-( 2-Mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-Mercaptoethylamine, 2-Mercaptoimidazole, 2-Mercaptobenzoimidazole, 2-Mercapto-3-pyridinol, 2-Mercaptobenzothiazole, Mercaptoacetic acid, Trimethylol propanthris (3-mercaptopropionate), Pentaerythritol tetrakis A mercapto compound such as (3-mercaptopropionate), a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid. Alkyl iodide compounds such as, trimethylolpropanthris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio. Propionate, Butanediol bisthioglycolate, Ethyleneglycol bisthioglycolate, Trimethylol propanetristhioglycolate, Butanediol bisthiopropionate, Trimethylol propanetristhiopropionate, Trimethylol propanetristhioglycolate , Pentaerythritol tetraxthiopropionate, pentaerythritol tetraxthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, and Karenz MT BD1, PE1, NR1 manufactured by Showa Denko KK.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphate and perfluoroalkyl carboxylate; 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 can also be used in combination.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, and octyl as silane coupling agents having an alkenyl group. Examples thereof include tenyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, and examples of the silane coupling agent having an acrylic group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane. Examples of the silane coupling agent having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like. Examples thereof include methacryloxioctyltrimethoxysilane, and examples of the silane coupling agent having an epoxy group include 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Examples thereof include xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxyoctyltrimethoxysilane, and N. -2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N -(Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and the like can be mentioned, and tris- (trimethoxysilylpropyl) isocyanurate can be mentioned as a silane coupling agent having an isocyanurate group. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like, and ureido groups. Examples of the silane coupling agent having a sulfide group include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane, and examples of the silane coupling agent having a sulfide group include bis (triethoxysilylpropyl) tetrasulfide. As a silane coupling agent having a thioester group, 3-octanoylthio-1-propyltriethoxysilane can be mentioned, and as a silane coupling agent having an isocyanate group, 3-isocyanatepropyltriethoxysilane and 3-isocyanidepropyltrimethoxysilane. And so on.

Commercially available products can be used as the above silane coupling agent, and examples thereof include KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd. and Montive Performance Materials Japan LLC as vinyl trimethoxysilane. A-171, Z-6300 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL XL10 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., Sila Ace S210 manufactured by Himi Shoji Co., Ltd., and the like. KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., A-151 manufactured by Montive Performance Materials Japan LLC, Z-6519 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL manufactured by Asahi Kasei Wacker Silicone Co., Ltd. GF56, Sila Ace S220 manufactured by Himi Shoji Co., Ltd., etc., as vinyl triacetoxysilane, GENIOSIL GF62 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as vinyl tris (2-methoxyethoxy) silane, Montive. A-172 manufactured by Performance Materials Japan LLC is mentioned, and examples of vinylmethyldimethoxysilane are A-2171 manufactured by Montive Performance Materials Japan LLC and GENIOSIL XL12 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Examples of the octenyltrimethoxysilane include KBM-1083 manufactured by Shin-Etsu Chemical Co., Ltd., and examples of the allyltrimethoxysilane include Z-6825 manufactured by Toray Dow Corning Co., Ltd. , P-styryltrimethoxysilane, KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd., and 3-acryloxypropyltrimethoxysilane, KBM-5103, 3-methacryloxypropylmethyldimethoxy. Examples of the silane include KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd. and Z-6033 manufactured by Toray Dow Corning Co., Ltd., and 3-methacryloxypropyltrimethoxysilane is Shin-Etsu Chemical Co., Ltd. KBM-503 manufactured by Montive Performance Materials Japan LLC, A-174 manufactured by Montive Performance Materials Japan LLC, Z-6030 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL GF31 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., Himi Shoji Co., Ltd. Examples thereof include Syrah Ace S710 manufactured by the company, and 3-methacryloxypropylmethyldiethoxysilane. Examples include KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd., and 3-methacryloxypropyltriethoxysilane includes KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd. and Montive Performance Materials Japan. Y-9936 manufactured by the company can be mentioned, and KBM-5803 manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned as the methacryloxyoctyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane can be mentioned as the 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd., A-186 manufactured by Montive Performance Materials Japan LLC, Z-6043 manufactured by Toray Dow Corning Co., Ltd., Sila Ace manufactured by Himi Shoji Co., Ltd. Examples of 3-glycidoxypropylmethyldimethoxysilane include KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6044 manufactured by Toray Dow Corning Co., Ltd., and Himi Shoji Co., Ltd. Examples include Sila Ace S520 and the like. Examples of 3-glycidoxypropyltrimethoxysilane are KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., A-187 manufactured by Montive Performance Materials Japan LLC, and Toray Dow. Examples include Z-6040 manufactured by Corning Co., Ltd., GENIOSIL GF80 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., Sila Ace S510 manufactured by Himi Shoji Co., Ltd., and Shin-Etsu Chemical Co., Ltd. as 3-glycidoxypropylmethyldiethoxysilane. KBE-402 manufactured by Kogyo Co., Ltd. can be mentioned. Examples of 3-glycidoxypropyltriethoxysilane are KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd. and A manufactured by Montive Performance Materials Japan LLC. -1871, GENIOSIL GF82 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., etc., and KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd. as glycidoxyoctyltrimethoxysilane, N-2- (amino). As ethyl) -3-aminopropylmethyldimethoxysilane, KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd., A-2120 manufactured by Montive Performance Materials Japan LLC, and GENIOSIL manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Examples thereof include GF-95 and Sila Ace S310 manufactured by Himi Shoji Co., Ltd., and examples of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane are KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd. , A-1120 manufactured by Montive Performance Materials Japan LLC, A-1122 manufactured by Montive Performance Materials Japan LLC, Z-6020 manufactured by Toray Dow Corning Co., Ltd., Toray Dow Corning Z-6094 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., GENIOSIL GF-91 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., Sila Ace S320 manufactured by Himi Shoji Co., Ltd., etc. KBM-903 manufactured by Montive Performance Materials Japan Co., Ltd., A-1110 manufactured by Montive Performance Materials Japan LLC, Z-6610 manufactured by Toray Dow Corning Co., Ltd., Sila Ace S360 manufactured by Himi Shoji Co., Ltd., etc. , 3-Aminopropyltriethoxysilane, KBE-903, A-1100 manufactured by Montive Performance Materials Japan LLC, Z-6011 manufactured by Toray Dow Corning Co., Ltd., manufactured by Himi Shoji Co., Ltd. Sila Ace S330 and the like, and examples of 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine include KBE-9103 and Sila Ace S340 manufactured by Himi Shoji Co., Ltd. As phenyl-3-aminopropyltrimethoxysilane, KBM-573 manufactured by Shinetsu Chemical Industry Co., Ltd., Y-9669 manufactured by Montive Performance Materials Japan GK, and Z manufactured by Toray Dow Corning Co., Ltd. Examples of N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine include Sila Ace XS1003 manufactured by Himi Shoji Co., Ltd., and N- (vinylbenzyl) -2-amino. As the hydrochloride salt of ethyl-3-aminopropyltrimethoxysilane, KBM-575 manufactured by Shinetsu Chemical Industry Co., Ltd., Z-6032 manufactured by Toray Dow Corning Co., Ltd., Sila Ace S350 manufactured by Himi Shoji Co., Ltd., etc. As the tris- (trimethoxysilylpropyl) isocyanurate, KBM-9569 manufactured by Shin-Etsu Chemical Industry Co., Ltd. can be mentioned, and as 3-mercaptopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBM-802, Z-6852 manufactured by Toray Dow Corning Co., Ltd., and KBM-803 manufactured by Shin-Etsu Chemical Industry Co., Ltd. as 3-mercaptopropyltrimethoxysilane, jointly with Montive Performance Materials Japan Examples include A-189 manufactured by the company, Z-6062 manufactured by Toray Dow Corning Co., Ltd., Sila Ace S810 manufactured by Himi Shoji Co., Ltd., and Montive Performance Materials as 3-mercaptopropyltriethoxysilane. -A-1891 manufactured by Japan GK, Z-6911 manufactured by Toray Dow Corning Co., Ltd., and A- of 3-ureidopropyltriethoxysilane manufactured by Montive Performance Materials Japan GK. 1160 is mentioned, examples of 3-ureidopropyltrialkoxysilane are KBE-585 manufactured by Shin-Etsu Chemical Industry Co., Ltd., and examples of bis (triethoxysilylpropyl) tetrasulfide are manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBE-846 is mentioned, as 3-octanoylthio-1-propyltriethoxysilane, A-LINK599 manufactured by Montive Performance Materials Japan LLC is mentioned, and as 3-isocyanylthio-1-propyltriethoxysilane, Shinetsu KBE-9007 manufactured by Kagaku Kogyo Co., Ltd., A-1310 manufactured by Montive Performance Materials Japan GK, etc. can be mentioned. Examples thereof include Y-5187 manufactured by the company and GENIOSIL GF40 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.

Among these silane coupling agents, silane coupling agents having a methacryloyl group, an epoxy group or an isocyanate group are preferably used, and for example, KBM-502, KBE-403 and KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd. And so on.

Examples of the melamine compound include all or a part _{of active methylol groups (CH 2} OH groups) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylolglycoluryl, (poly) methylolbenzoguanamine, and (poly) methylolurea. Examples thereof include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be the same as each other or may be different from each other. In addition, the methylol group that has not been alkyl etherized may be self-condensed within one molecule, or may be condensed between two molecules, resulting in the formation of an oligomer component.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluryl, tetrabutoxymethylglycoluryl and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

The photosensitive composition of the present invention is 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 and dipping. It can be applied on a supporting substrate such as. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

Further, as the light source of the energy ray 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 steam arc lamp, a xenon arc lamp, etc. High electromagnetic energy, electron beam, X-ray, radiation, etc. with wavelengths of 2000 angstrom to 7000 angstrom obtained from carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc. Although energy rays can be used, preferred examples thereof include an ultrahigh pressure mercury lamp, a mercury steam arc lamp, a carbon arc lamp, and a xenon arc lamp that emit light having a wavelength of 300 to 450 nm.

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

Further, the photosensitive composition of the present invention can also be used for creating patterns having different steps and heights using a halftone mask.

The photosensitive composition of the present invention is a photocurable paint or varnish; a photocurable adhesive; a printed substrate; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a mobile information terminal, or a digital camera; a CCD. Image sensor color filter; electrode material for plasma display panel; powder coating; printing ink; printing plate; adhesive; dental composition; gel coat; photoresist for electronic engineering; electroplating resist; etching resist; dry film; Solder resist; resist 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. Object; Solder resist; Magnetic recording material; Micromechanical parts; Waveguide; Optical switch; Plating mask; Etching mask; Color test system; Glass fiber cable coating; Screen printing stencil; Three-dimensional object manufactured by stereolithography Materials for holography recording; Image recording materials; Microelectronic circuits; Decolorizing materials; Decolorizing materials for image recording materials; Decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; Photoresist material for UV and visible laser direct imaging system; Can be used for various applications such as photoresist material or protective film used for forming a dielectric layer in sequential lamination of printed circuit substrates, and is particularly limited to that application. There is no.

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 forming a protrusion for a vertically oriented liquid crystal display element. In particular, it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for a vertically oriented liquid crystal display element.

The above 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) irradiating the coating film with radiation through a mask having a predetermined pattern shape. It is preferably formed by a step of (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 is added is useful as a partition forming resin composition for an inkjet method, and the composition is used for a color filter, especially when the profile angle is 50 ° or more. It is preferably used for a partition wall for an inkjet color filter. As the ink repellent, a composition composed of a fluorine-based surfactant and a fluorine-based surfactant is preferably used.

An optical element is formed by a method in which a partition wall formed from the photosensitive composition of the present invention partitions on a transfer target, and droplets are applied to recesses on the partitioned transfer target by an inkjet method to form an image region. Manufactured. At this time, it is preferable that the droplets contain a colorant and the image region is colored, and at least a partition wall that separates a pixel group composed of a plurality of colored regions and each colored region of the pixel group is provided on the substrate. An optical element having and manufactured by the above-mentioned method for manufacturing an optical element is preferably used.

The photosensitive composition of the present invention is also used as a protective film or a composition for an insulating film, and contains an ultraviolet absorber, an alkylation-modified melamine and / or an acrylic-modified melamine, and an alcoholic hydroxyl group in the molecule. (Meta) acrylate monomer and / or silica sol can be contained.

Examples of the photosensitive composition for the protective film and the insulating film include, for example.
(I) A carboxyl group-containing resin obtained by reacting a diol compound with a polyvalent carboxylic acid and having a weight average molecular weight of 2,000 to 40,000 and an acid value of 50 to 200 mgKOH / g.
(II) An unsaturated compound containing at least one photopolymerizable ethylenically unsaturated bond in one molecule.
A resin composition containing (III) an epoxy compound and (IV) a photopolymerization initiator component as main components.
The component (III) is contained in an amount of 10 to 40 parts by weight, the component (IV) is contained in an amount of 0.01 to 2.0 parts by weight, and (IV) is contained in a total of 100 parts by weight of the component (I) and the component (II). ) Component Photopolymerization Initiator A resin composition using the photopolymerization initiator composition of the present invention is used as a component.

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

The 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 wall pattern, a dielectric pattern, an electrode pattern and a black matrix pattern of a plasma display panel.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In the following Examples and Comparative Examples,% is based on mass unless otherwise specified.

[Example 1]
In the compounding ratios shown in Table 1, the photopolymerization initiator composition No. 1 was prepared. As the component (A) and the component (B), those shown below were used.
Furthermore, SPC-1000 (acrylic resin; manufactured by Showa Denko Co., Ltd.) 55.46 parts by mass, Aronix M-450 (polyfunctional acrylate; manufactured by Toa Synthetic Co., Ltd.) 12.91 parts by mass, KBE-403 (silane coupling agent; Shinetsu). (Silicone) 0.58 parts by mass, FZ-2122 (initiator; Nippon Unicar) cyclohexanone 1% solution 3.23 parts by mass and propylene glycol-1-monomethyl ether-2-acetate 27.48 parts by mass , And the photopolymerization initiator composition No. 0.34 parts by mass of No. 1 was blended so that the total amount was 100 parts by mass, and the mixed solution was stirred well to obtain the alkaline developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. I got 1.
The obtained alkali-developable photosensitive resin composition No. Regarding No. 1, the sensitivity was evaluated by the following sensitivity evaluation method, and the resolution was evaluated by the following resolution evaluation method. The results of each are shown in Table 1.

[Examples 2 to 13]
In the compounding ratios shown in Table 1, the photopolymerization initiator composition No. 2-No. 13 was prepared. As the component (A) and the component (B), those shown below were used. Further, the photopolymerization initiator composition No. 1 used in Example 1. Alkali-developable photosensitive resin composition No. 1 was used in the same manner as in Example 1 except that these photopolymerization initiator compositions were used instead of 1. 2-No. I got 13. The sensitivity of the obtained alkali-developable photosensitive resin composition was evaluated by the following sensitivity evaluation method, and the resolution was evaluated by the following resolution evaluation method. The results of each are shown in Table 1.

[Comparative Examples 1 to 15]
In the compounding ratios shown in Table 2, the comparative photopolymerization initiator composition No. 1-No. 15 was prepared. As the comparative photopolymerization initiators -1 and -2, those shown below were used.
Further, the photopolymerization initiator composition No. 1 used in Example 1. Comparative Alkali Developable Photosensitive Resin Composition No. 1 in the same manner as in Example 1 except that these comparative photopolymerization initiator compositions were used instead of 1. 1-No. I got 15. The sensitivity of the obtained alkali-developable photosensitive resin composition was evaluated by the following sensitivity evaluation method, and the resolution was evaluated by the following resolution evaluation method. The results of each are shown in Table 2.

[(A) component]
As the component (A), the following compound No. 1. Compound No. 6 and compound No. 11 was used.

[Component (B)]
As the component (B), the following compound No. 13. Compound No. 15. And Compound No. 21 was used.

[Comparative photopolymerization initiator]
The following comparative photopolymerization initiator-1 and comparative photopolymerization initiator-2 were used in Comparative Examples.

<Sensitivity evaluation method>
The sensitivity of the obtained alkali-developable photosensitive resin composition and the comparative alkali-developable photosensitive resin composition was evaluated as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated on a glass substrate, prebaked at 90 ° C. for 90 seconds using a hot plate, and exposed through a mask using a high-pressure mercury lamp as a light source. After development using a 2.5 mass% sodium carbonate aqueous solution as a developing solution, it was washed well with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. The pattern for an exposure amount of 40 mJ was observed with an electron microscope, and the line width of the mask opening of 20 μm was measured. A line width of 21 μm or more was designated as A, 20 to 21 μm was designated as B, 19 to 20 μm was designated as C, and a line width of 19 μm or less was designated as D. A has the highest sensitivity, followed by B and C, and D has the lowest sensitivity.

<Resolution evaluation method>
The resolution evaluation of the obtained alkali-developable photosensitive resin composition and the comparative alkali-developable photosensitive resin composition was carried out as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated on a glass substrate, prebaked at 90 ° C. for 90 seconds using a hot plate, and exposed through a mask using a high-pressure mercury lamp as a light source. After development using a 2.5 mass% sodium carbonate aqueous solution as a developing solution, it was washed well with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. The pattern when the residual film sensitivity (residual film ratio 75%) was adjusted was observed with an electron microscope, and the line width of the mask opening of 20 μm was measured. The difference between the mask opening and the line width of 0.5 μm or less was defined as A, the difference of 0.5 to 1.0 μm was defined as B, the difference of 1.0 to 2.0 μm was defined as C, and the difference of 2.0 μm or more was defined as D. A has the highest resolution, followed by B and C, and D has the lowest resolution.

According to the present invention, it is possible to provide a photopolymerization initiator composition capable of imparting excellent sensitivity and resolution to a photosensitive composition. Further, according to the present invention, it is possible to provide a photosensitive composition having excellent sensitivity and resolution.

Claims (7)

A photopolymerization initiator composition containing 1 to 99 parts by mass of the following component (A) and 1 to 99 parts by mass of the following component (B) (however, the total of the components (A) and (B) is 100 parts by mass).
Component (A): Consists of one or more of the oxime ester compounds represented by the following general formulas (1-1) to (1-3), which have an ether structure represented by the following general formula (3). Photopolymerization initiator.

In the general formulas (1-1) to (1-3), R ¹ , R ² and R ⁶ are independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and carbon. Represents an aryl group having 6 to 30 atoms, an aryloxy group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group or a cyano group having 2 to 20 carbon atoms, and an alkyl group or an alkoxy group. The hydrogen atoms of the group, aryl group, aryloxy group, aralkyl group and heterocyclic group are further OR ¹¹ , COR ¹¹ , SR ¹¹ , NR ¹² R ¹³ , -NCOR ^{12- OCOR 13} , CN, halogen atom, -CR ¹¹ = CR ¹² R ¹³ or -CO-CR ¹¹ = CR ¹² R ¹³ may be substituted, and R ¹¹ , R ¹² and R ¹³ are independently alkyl hydrogen atoms and 1 to 20 carbon atoms, respectively. Represents a group, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and represents R ¹ , R ² , R ⁶ , R ¹¹ , R ^{12 above.} And ^{the alkylene moiety of the substituent represented by R 13} may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl moiety of the group may have a branched side chain, it may be cyclic alkyl, the alkyl end of the substituent may be an unsaturated bond, and R ² is combined with the adjacent benzene ring. May form a ring.
R ³ , R ⁴ and R ⁵ independently have an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 6 to 30 carbon atoms. Represents an aryloxy group, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and The hydrogen atoms of the heterocyclic group are further OR ¹⁴ , COR ¹⁴ , SR ¹⁴ , NR ¹⁵ R ¹⁶ , -NCOR ¹⁵ -OCOR ¹⁶ , CN, halogen atom, -CR ¹⁴ = CR ¹⁵ R ¹⁶ or -CO-CR ¹⁴ = CR ¹⁵ R ¹⁶ may be substituted, and R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms, respectively. It represents an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and is an alkylene moiety of a substituent represented by ^{R 3} , R ⁴ , R ⁵ , R ¹⁴ , R ¹⁵ and R ^{16 above.} May be interrupted 1 to 5 times by unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane bond, and the alkyl moiety of the above substituent may have a branched side chain. Yes, it may be cyclic alkyl, the alkyl end of the substituent may be an unsaturated bond, and a, b and d are independently integers from 0 to 3.
A ¹ is represented by the above general formula (3), and in the general formula (3), R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The hydrogen atom of the alkyl group may be substituted with a halogen atom, and the methylene group of the alkylene portion of the alkyl group is 1 due to an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. It may be interrupted ~ 5 times, the alkyl moiety may have a branched side chain, it may be cyclic alkyl, the alkyl terminal may be unsaturated, and R ⁷ and R ⁸ may be They may form a ring together.
Component (B): A photopolymerization initiator containing one or more of the oxime ester compounds represented by the following general formula (2-2) , which has the cycloalkyl structure of the following general formula (4).

In the general formula (2-2), R ²¹ is an alkyl group having carbon atom number of 1 to 20, an alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, carbon atoms 6 to 30 Represents an aryloxy group, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group or a cyano group having 2 to 20 carbon atoms, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and a heterocyclic group. The hydrogen atoms of are further OR ³¹ , COR ³¹ , SR ³¹ , NR ³² R ³³ , -NCOR ³² -OCOR ³³ , CN, halogen atoms, -CR ³¹ = CR ³² R ³³ or -CO-CR ³¹ = CR ³² R. It may be substituted with ^{33 , and R 31} , R ³² and R ³³ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and carbon atoms, respectively. The alkylene moiety of the substituent representing 7 to 30 aralkyl groups or heterocyclic groups having 2 to 20 carbon atoms and represented by R ²¹ , R ³¹ , R ³² and R ³³ is an unsaturated bond, an ether bond, and the like. It may be interrupted 1 to 5 times by a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl moiety of the above substituent may have a branched side chain or may be a cyclic alkyl. , alkyl terminus of the substituents there Ru if unsaturated bond.
R ²³ and R ²⁴ independently have an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aryloxy having 6 to 30 carbon atoms. Represents a group, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and a heterocyclic group. The hydrogen atoms of are further OR ³⁴ , COR ³⁴ , SR ³⁴ , NR ³⁵ R ³⁶ , -NCOR ^{35- OCOR 36} , CN, halogen atom, -CR ³⁴ = CR ³⁵ R ³⁶ or -CO-CR ³⁴ = CR ³⁵ R. It may be substituted with ^{36 , and R 34} , R ³⁵ and R ³⁶ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and carbon atoms, respectively. The alkylene moiety of the substituent representing 7 to 30 aralkyl groups or heterocyclic groups having 2 to 20 carbon atoms and represented by R ²³ , R ²⁴ , R ³⁴ , R ³⁵ and R ^{36 is an unsaturated bond.} It may be interrupted 1 to 5 times by an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl moiety of the above substituent may have a branched side chain and is cyclic alkyl. In some cases, the alkyl end of the substituent may be an unsaturated bond, where u and v are independently integers from 0 to 3 .
L ¹ represents a hydrogen atom or a benzoyl group,
G ¹ represents the group of the general formula (4), in which n is an integer of 1 to 5 and m is an integer of 1 to 6. A photosensitive composition obtained by incorporating the photopolymerization initiator composition according to claim 1 into a polymerizable compound having an ethylenically unsaturated bond. The photosensitive composition according to claim 2, further comprising an inorganic compound. The photopolymerization initiator composition according to claim 1 is contained in an alkali-developable compound that may have an ethylenically unsaturated bond and a polymerizable compound that has an ethylenically unsaturated bond. Photopolymer composition. The alkali-developable photosensitive resin composition according to claim 4, further comprising an inorganic compound. A colored alkali-developable photosensitive resin composition obtained by further adding a coloring material to the alkali-developable photosensitive resin composition according to claim 4 or 5. The photosensitive composition according to claim 2 or 3, the alkali-developable photosensitive composition according to claim 4 or 5, or the colored alkali-developable photosensitive resin composition according to claim 6 is irradiated with energy rays. Hardened product.