JP6688087B2 - Compound, composition and photopolymerization initiator - Google Patents

Description

  The present invention provides a novel compound, a composition containing the compound, a photopolymerization initiator containing the composition, and a photosensitizer containing the polymerizable compound having an ethylenically unsaturated bond in the photopolymerization initiator. Sex composition.

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

  As a photopolymerization initiator used in the photosensitive composition, Patent Documents 1 to 11 propose to use an oxime ester compound. A colored alkali-developable photosensitive resin composition containing a color material such as a color filter is required to have high sensitivity, and it is necessary to make the photopolymerization initiator in the resist have a high concentration. The oxime ester compound described in 11 was not sufficiently soluble in a solvent.

Japanese Patent Laid-Open No. 2000-80068 JP 2001-233842 A JP 2001-302871 A Specification No. 2004-534797 JP 2005-25169 A JP-A-2005-128483 JP-A-2005-242279 JP-A-2005-242280 JP 2006-16545 A JP 2008-3164 A Japanese Patent No. 3754065

  A colored alkali-developable photosensitive resin composition containing a color material such as a color filter is required to have high sensitivity, and it is necessary to increase the concentration of the photopolymerization initiator in the resist. The photopolymerization initiator does not have sufficient solubility in a solvent, and it was difficult to increase the concentration in the resist. The cross-sectional shape of the cured product obtained by polymerizing and curing the photosensitive resin composition is preferably such that the width of the lower part of the cured product is larger than the width of the upper part of the cured product. It is known that when this cross-sectional shape is obtained, the cured product is less likely to collapse and the cured product is less likely to peel off. There has been a demand for a photosensitive composition, an alkali-developable photosensitive resin composition, and a colored alkali-developable photosensitive resin composition which have properties satisfying these requirements.

  Therefore, an object of the present invention is to provide a photopolymerization initiator having high solubility in a solvent, and a photosensitive material in which the cross-sectional shape of a cured product when polymerized and cured is such that the width of the cured product lower part is larger than the width of the cured product upper part. The present invention provides a novel compound used for obtaining a photosensitive composition, an alkali-developable photosensitive resin composition and a colored alkali-developable photosensitive resin composition. The present invention also provides the above-mentioned photopolymerization initiator, photosensitive composition, alkali-developable photosensitive resin composition and colored alkali-developable photosensitive resin composition.

  The present invention includes a novel compound represented by the following general formula (I), a photopolymerization initiator containing the compound, a composition containing the compound and a compound represented by the following general formula (II), and the composition: The above object is achieved by providing a photopolymerization initiator containing a substance.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、
Ｒ¹¹、Ｒ¹²及びＲ¹³は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数３〜２０のシクロアルキル基、炭素原子数４〜２０のシクロアルキルアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ¹¹、Ｒ¹²及びＲ¹³で表わされる置換基の水素原子は、更にＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＮＲ²²Ｒ²³、ＣＯＮＲ²²Ｒ²³、−ＮＲ²²−ＯＲ²³、−ＮＣＯＲ²²−ＯＣＯＲ²³、−Ｃ（＝Ｎ−ＯＲ²¹）−Ｒ²²、−Ｃ（＝Ｎ−ＯＣＯＲ²¹）−Ｒ²²、ＣＮ、ハロゲン原子、又はＣＯＯＲ²¹で置換されている場合もあり、
Ｒ²¹、Ｒ²²及びＲ²³は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ²¹、Ｒ²²及びＲ²³で表される置換基の水素原子は、更にＣＮ、ハロゲン原子、水酸基又はカルボキシル基で置換されている場合もあり、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基のアルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ²⁴−、−ＮＲ²⁴ＣＯＯ−、−ＯＣＯＮＲ²⁴−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断されている場合もあり、
Ｒ²⁴は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基のアルキル部分は、分岐側鎖がある場合があり、環状アルキルである場合があり、また、Ｒ¹²とＲ¹³及びＲ²²とＲ²³はそれぞれ一緒になって環を形成する場合があり、
Ｚ¹は、結合手であって、単結合、−Ｏ−、−Ｓ−、−ＮＲ²²−、−ＮＲ²²ＣＯ−、−ＳＯ₂−、−ＣＳ−、−ＯＣＯ−又は−ＣＯＯ−を表し、
Ｚ²は、結合手であって、単結合、炭素原子数１〜２０のアルカンジイル基、炭素原子数６〜３０のアリールジイル基、炭素原子数７〜３０のアリールアルキルジイル基又は炭素原子数２〜２０の２価の複素環基を表し、
Ｚ²で表される結合手のアルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ²²−、−ＮＲ²²ＣＯＯ−、−ＯＣＯＮＲ²²−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断されている場合があり、Ｚ²で表される結合手のアルキレン部分は分岐側鎖がある場合があり、環状アルキレンである場合があり、
Ｘは下記化学式（Ｉ−Ａ）又は（Ｉ−Ｂ）で表される結合手を表す。）

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN;
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, Represents an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom of the substituent represented by R ¹¹ , R ¹² and R ¹³ is further represented by OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR ²² —OCOR. ^{23, -C (= N-oR} 21) -R 22, -C (= N-OCOR 21) -R 22, CN, there halogen atom, or may have been substituted by COOR ^21,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic group of the number 2 to 20,
The hydrogen atom of the substituent represented by R ²¹ , R ²² and R ²³ may be further substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,
The alkylene portion of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, — ^{NR 24 COO -, - OCONR 24} -, - SCO -, - COS -, - OCS- or -CSO- by may have been interrupted 1-5 times,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. ,
The alkyl part of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ may have a branched side chain, may be cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ may combine together to form a ring,
Z ¹ is a bond and represents a single bond, —O—, —S—, —NR ²² —, —NR ²² CO—, —SO ₂ —, —CS—, —OCO— or —COO—. ,
Z ² is a bond and is a single bond, an alkanediyl group having 1 to 20 carbon atoms, an aryldiyl group having 6 to 30 carbon atoms, an arylalkyldiyl group having 7 to 30 carbon atoms, or 2 carbon atoms. Represents a divalent heterocyclic group of 20
Alkylene moiety of bond represented by Z ² is, -O -, - S -, - COO -, - OCO -, - NR 22 -, - NR 22 COO -, - OCONR 22 -, - SCO -, - It may be interrupted 1 to 5 times by COS-, -OCS- or -CSO-, the alkylene portion of the bond represented by Z ² may have a branched side chain, and may be cyclic alkylene. Yes,
X represents a bond represented by the following chemical formula (IA) or (IB). )

（式（Ｉ−Ａ）及び（Ｉ−Ｂ）中、＊は結合手を表す。）

(In formulas (IA) and (IB), * represents a bond.)

（式中、Ｒ¹、Ｒ²、Ｚ¹及びＺ²は一般式（Ｉ）中のＲ¹、Ｒ²、Ｚ¹及びＺ²と同義であり、Ｚ^aはＯＨ又はＣＯＯＨを表す。）

(Wherein, is R ^1, R ^2, Z ¹ and Z ² R ¹ in the general formula (I), R ^2, the same meaning as Z ¹ and Z ^2, Z ^a represents OH or COOH.)

The present invention also provides a photosensitive composition comprising the above photopolymerization initiator containing a polymerizable compound having an ethylenically unsaturated bond.
The present invention also provides an alkali-developable photosensitive resin composition comprising the above-mentioned photosensitive composition containing a compound having an alkali-development property which may have an ethylenically unsaturated group.
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 above-mentioned photosensitive composition, alkali-developable photosensitive resin composition, or colored alkali-developable photosensitive resin composition with energy rays.

  By using the novel compound of the present invention in combination with the compound represented by the above general formula (II), the photopolymerization initiator having high solubility in a solvent and the cross-sectional shape of the cured product when polymerized and cured are cured. A novel composition used for obtaining a photosensitive composition having a shape in which the width of the cured product lower portion is larger than the width of the cured product upper portion, an alkali-developable photosensitive resin composition and a colored alkali-developable photosensitive resin composition. Obtainable. INDUSTRIAL APPLICABILITY The composition of the present invention has a high transmittance in the visible light region, is hard to sublime, has excellent developability, and can efficiently generate radicals for a bright line such as 365 nm (i-line). It is useful as a photopolymerization initiator used for a product.

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

The compound of the present invention is a novel compound represented by the above general formula (I). The compound has geometrical isomers due to the double bond of oxime, but does not distinguish them.
That is, in the present specification, the compound represented by the general formula (I), and the compound represented by the following general formula (III), which is a preferred form of the compound described below, and the exemplified compound thereof are a mixture of both or either. It represents one of them and is not limited to the structure showing isomers.

As the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ^{24 in} the general formula (I) and the general formula (II). Is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, Examples include isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.

The cycloalkyl group having 3 to 20 carbon atoms represented by R ¹¹ , R ¹² and R ¹³ in the general formula (I) and the general formula (II) is a saturated alkyl group having 3 to 20 carbon atoms. It means a monocyclic or saturated polycyclic alkyl group. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl.

The cycloalkylalkyl group having 4 to 20 carbon atoms represented by R ¹¹ , R ¹² and R ¹³ in the general formula (I) and the general formula (II) means at least one hydrogen atom in the alkyl group. Means a group having 4 to 20 carbon atoms substituted with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylethyl, cyclodecylethyl, adamantylpropyl and decahydronaphthyl. Propyl etc.

As the aryl group having 6 to 30 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ^{24 in} the above general formula (I) and general formula (II). Examples include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl and the like.

An arylalkyl group having 7 to 30 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ^{24 in} the above general formula (I) and general formula (II). Examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

A heterocyclic group having 2 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ^{24 in} the general formula (I) and the general formula (II). As, for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolydyl, thiazolydyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, Preferred examples thereof include 5- to 7-membered heterocycles such as morpholinyl.

Examples of the ring that can be formed by R ¹² and R ¹³ and R ²² and R ^{23 in the} general formula (I) and the general formula (II) together include, for example, a cyclopentane ring, a cyclohexane ring, and a cyclopentene ring. Preferred are 5- to 7-membered rings such as benzene ring, piperidine ring, morpholine ring, lactone ring and lactam ring.

Z ² in the general formula (I) and the general formula (II) represents an alkanediyl group having 1 to 20 carbon atoms, an aryldiyl group having 6 to 30 carbon atoms, and an arylalkyldiyl having 7 to 30 carbon atoms. Represents a group or a divalent heterocyclic group having 2 to 20 carbon atoms.

  Examples of the alkanediyl group having 1 to 20 carbon atoms include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene. , 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, Examples thereof include tridecylene, tetradecylene, pentadecylene, ethane-1,1-diyl, propane-2,2-diyl and the like.

  Examples of the aryldiyl group having 6 to 30 carbon atoms include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,4-naphthylene and 2,5-dimethyl. -1,4-phenylene, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenylsulfide-4,4'-diyl, diphenylsulfone-4,4'-diyl, etc. Is mentioned.

  Examples of the arylalkyldiyl group having 7 to 30 carbon atoms include arylalkylene groups such as a linking group represented by [Chemical Formula 4].

  Examples of the divalent heterocyclic group having 2 to 20 carbon atoms include 2,5-pyridinediyl, 2,6-pyridinediyl, 2,5-pyrimidinediyl, 2,5-thiophenediyl and 3 , 4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazoldiyl, 2,5-benzofurandiyl, 2,5-benzothiophenediyl, N-methylindole-2,5 Examples thereof include divalent heterocyclic groups such as -diyl, 2,5-benzothiazolediyl and 2,5-benzoxazolediyl.

Further, a halogen atom which may substitute the hydrogen atom of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the above general formula (I) and general formula (II). Examples thereof include fluorine, chlorine, bromine and iodine.

In the general formula (I) and the general formula (II), the alkylene moiety of the substituents represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is —O—, —S—, -COO -, - OCO -, - NR 24 -, - NR 24 COO -, - OCONR 24 -, - SCO -, - COS -, - OCS- or -CSO- by may be interrupted 1 to 5 times The binding group interrupted at this time may be one kind or two or more kinds of groups, and in the case of a group capable of being interrupted continuously, two or more may be interrupted continuously. The alkylene moiety of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the above general formulas (I) and (II) may have a branched side chain. Yes, and may be cyclic alkyl.

The alkylene moiety of the bond represented by Z ² in the general formula (I) and the general formula (II) is —O—, —S—, —COO—, —OCO—, —NR ²² —, —NR. ^{22 COO -, - OCONR 22 -} , - SCO -, - COS -, - OCS- or -CSO- by may be interrupted 1 to 5 times, this time interrupting linking groups one or more It may be a group, and in the case of a group which can be interrupted continuously, two or more may be interrupted continuously. The alkylene portion of the bond represented by Z ² in the above general formulas (I) and (II) may have a branched side chain or may be cyclic alkyl.

X in the general formula (I) represents a bond represented by the chemical formula (IA) or (IB). Further, Z ^a in the general formula (II) represents OH or COOH.

Among the compounds represented by the above general formula (I), those in which R ¹ and R ² are a methyl group or a phenyl group or those represented by the following general formula (III) are represented by the above general formula (II). When used in combination with the compound represented by, the photosensitivity is such that the cross-sectional shape of the cured product when polymerized and cured is higher than the width of the upper part of the cured product when it is polymerized and cured. It is particularly preferable because the effect of obtaining the composition is high. Two R ^{1 s} in the general formula (I) may be the same or different. Further, two R ^{2 s} in the general formula (I) may be the same or different. The two R ¹ are preferably the same. Similarly, the two R ² are preferably the same.

（式中、Ｒ¹、Ｒ²、Ｚ¹、Ｚ²及びＸは一般式（Ｉ）中のＲ¹、Ｒ²、Ｚ¹及びＺ²と同義である。）

(In the formula, R ¹ , R ² , Z ¹ , Z ² and X have the same meanings as R ¹ , R ² , Z ¹ and Z ^{2 in} formula (I).)

  Therefore, preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compound No. 1-No. 70 is mentioned. However, the present invention is not limited to the following compounds.

The compound represented by the general formula (I) can be produced by dimerizing an oxime ester compound having a specific structure having a hydroxyl group or a carboxyl group. The method for producing the above specific oxime estem compound is not particularly limited, but can be produced, for example, by the method described in JP-A-2000-80068. As one of the methods, there is a method of producing by the following method.
That is, the oxime compound 2 is obtained by reacting the ketone body 1 and the nitrite ester in the presence of hydrochloric acid. Subsequently, the oxime compound 2 is reacted with an acid anhydride 3 or an acid chloride 3 ′ to form an oxime having a specific structure having a hydroxyl group or a carboxyl group as a raw material for the compound represented by the general formula (I). An ester compound can be obtained. The compound represented by the above general formula (I) can be produced by dimerizing this with a catalyst or by dehydration condensation.

  The composition of the present invention comprises (A) a compound represented by the above general formula (I) (hereinafter sometimes abbreviated as component A); and (B) a compound represented by the above general formula (II) ( Hereinafter, it may be abbreviated as component B). The composition of the present invention has a very high solubility in a solvent, a high transmittance in the visible light region, a low sublimation property, an excellent developability, and an efficient radical for a bright line such as 365 nm (i-line). Therefore, it is useful as a photopolymerization initiator used in the photosensitive composition.

The component (A) of the composition of the present invention is a compound represented by the general formula (I) in which R ¹ and R ² are a methyl group or a phenyl group, or a compound represented by the general formula (III). Those which are compounds are preferred. In this case, it is possible to obtain a composition having a high solubility in a solvent, and a photosensitive composition in which the cross-sectional shape of the cured product when polymerized and cured is such that the width of the cured product lower part is larger than the width of the cured product upper part. Can be obtained.

The component (B) of the composition of the present invention is a compound represented by the general formula (II), wherein R ¹ and R ² are a methyl group or a phenyl group, or a compound represented by the following general formula (IV). Those which are compounds are preferred. In this case, it is possible to obtain a composition having a high solubility in a solvent, and a photosensitive composition in which the cross-sectional shape of the cured product when polymerized and cured is such that the width of the cured product lower part is larger than the width of the cured product upper part. Can be obtained.

（式中、Ｒ¹、Ｒ²、Ｚ¹、Ｚ²及びＺ^aは一般式（ＩＩ）中のＲ¹、Ｒ²、Ｚ¹Ｚ²及びＺ^aと同義である。）

^{(Wherein, R 1, R 2, Z} 1, Z 2 and Z ^a have the same meanings as formula (R ¹ in ^{II), R 2, Z 1} Z 2 and Z ^a.)

Among the compositions of the present invention, the component (A) is a compound in which R ¹ and R ² are methyl groups or phenyl groups or a compound represented by the general formula (III), and the component (B) is R ¹ and A composition in which R ² is a methyl group or a phenyl group or a compound represented by the above general formula (IV) can give a composition having particularly high solubility in a solvent, and when it is polymerized and cured, It is particularly preferable because it is possible to obtain a photosensitive composition in which the cross-sectional shape of the cured product is such that the width of the cured product lower portion is larger than the width of the cured product upper portion.

  The blending ratio of the A component and the B component in the composition of the present invention is not particularly limited, but the mass ratio is in the range of A component: B component = 0.001: 99.999 to 95: 5. In this case, the solubility in a solvent is high, and in the case of A component: B component = 0.01: 99.99 to 90:10, the solubility in a solvent is particularly high.

  Specific preferred examples of the compound represented by the general formula (II) include the following compound No. 71-No. 140 is mentioned. However, the present invention is not limited to the following compounds.

  The method for producing the compound represented by the general formula (II) is not particularly limited, but can be produced, for example, by the method described in JP-A-2000-80068. As one of the methods, there is a method of producing by the following method. That is, the oxime compound 2 is obtained by reacting the ketone body 1 and the nitrite ester in the presence of hydrochloric acid. Subsequently, the oxime compound 2 is reacted with the acid anhydride 3 or the acid chloride 3'to obtain the oxime ester compound represented by the general formula (II).

  The composition of the present invention described above is particularly useful as a photopolymerization initiator.

  The photopolymerization initiator of the present invention contains the compound of the present invention or the composition of the present invention, and is particularly useful as a photopolymerization initiator of a polymerizable compound having an ethylenically unsaturated bond. Among them, those containing the composition of the present invention are particularly preferable because they have high solubility and high sensitivity. The content of the compound of the present invention or the composition of the present invention in the photopolymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

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

The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in the photosensitive composition can be used, and examples thereof include ethylene, propylene, butylene, isobutylene, and vinyl chloride. Unsaturated vinyl hydrocarbons such as vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, Isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- Carboxypolycaprolactone mono (meth) acrylate or the like having a carboxy group and a hydroxyl group at both ends Limmer mono (meth) acrylate; having hydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 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 (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meth ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomer, and Esters of polyhydric alcohols or polyhydric phenols; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as oleic acid adducts, dodecenyl succinic anhydride, and methylhymic acid anhydride; (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) Amides of unsaturated monobasic acids and polyamines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as phenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenyl maleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane; vinyl chloride, vinylidene chloride, divinyls Vinylate compounds of vinyl chloride and vinylisocyanate compounds containing hydroxyl group, vinyl pyrrolidone, vinyl pyridine, vinyl pyrrolidone, vinyl pyridine, triallyl phosphate, triallyl phosphate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole Examples thereof include a vinyl epoxy compound containing vinyl monomer and polyepoxy compound.
Among these, a polymer mono (meth) acrylate having a carboxy group and a hydroxyl group at both ends, a polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups, and an unsaturated mono- A photopolymerization initiator containing the oxime ester compound of the present invention in an ester of a basic acid and a polyhydric alcohol or a polyhydric phenol is suitable.
These polymerizable compounds may be used alone or in admixture of two or more, and when two or more are mixed and used, they are preliminarily copolymerized and used as a copolymer. May be.

  The compound having alkali developability that may have an ethylenically unsaturated group is not particularly limited as long as it is soluble in an aqueous alkali solution, and examples thereof include the resins described in JP-A 2004-264414. .

The compound having alkali developability which may have an ethylenically unsaturated group is a copolymer of acrylic acid ester, phenol and / or cresol novolac epoxy resin, polyphenylmethane type having a polyfunctional epoxy group. A resin obtained by reacting an epoxy compound such as an epoxy resin, an epoxy acrylate resin, or an epoxy compound represented by the following general formula (IV) with an unsaturated monobasic acid and further with a polybasic acid anhydride is used. be able to.
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 (IV) and further allowing a polybasic acid anhydride to act is preferable.
Further, the compound having an alkali developability which may have an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

（式中、Ｘ¹は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、炭素原子数３〜２０の脂環式炭化水素基、Ｏ、Ｓ、ＳＯ₂、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ又は下記〔化２７〕、〔化２８〕若しくは〔化２９〕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てもよく、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＲ⁵⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｍは０〜１０の整数であり、ｍが０で無いときに存在する光学異性体は、どの異性体でもよい。）

(In the formula, X ¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO ₂ , SS, SO, CO, OCO or a substituent represented by the following [Chemical formula 27], [Chemical formula 28] or [Chemical formula 29], wherein the above alkylidene group may be substituted with a halogen atom, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom. The group and the alkenyl group may be substituted with a halogen atom, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.)

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

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

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

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

  Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl. Examples thereof include acrylate / malate and dicyclopentadiene / malate.

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

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is 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 1 epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct is The ratio of the acid anhydride structure of the polybasic acid anhydride to the number of the acid anhydrides is preferably 0.1 to 1.0.
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, comprises a photopolymerization initiator of the present invention as an essential component and a polymerization having an ethylenically unsaturated bond. Functional compound and a compound having an alkali developability which may have an ethylenically unsaturated group, and as an optional component, a combination of components such as an inorganic compound, a coloring material and a solvent. Among the alkali-developable photosensitive resin compositions of the present invention, those containing a coloring material are also particularly referred to as the colored alkali-developable photosensitive resin composition of the present invention.
The polymerizable compound having an ethylenically unsaturated bond and the compound having an alkali developability which may have an ethylenically unsaturated group may be the same compound, or may be different, , And may be used in combination of two or more.

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

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

When one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers are used as the polyfunctional epoxy compound, a (colored) alkali developable photosensitive resin composition having better properties can be obtained. Is preferable because it can
As the bisphenol type epoxy compound, the epoxy compound represented by the general formula (IV) can be used, and, for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other, novolac type epoxy compounds such as phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds; 3,4-epoxy-6-methyl Alicyclic epoxies 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; tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol, N, N-diglycidylaniline; etc .; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate; dicyclo Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds and the like can also be used.

  In the photosensitive composition of the present invention, the content of the photopolymerization initiator of the present invention is not particularly limited, but is preferably 1 with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. To 70 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 5 to 30 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 compound having alkali developability which may have an ethylenically unsaturated bond is In the (colored) alkali development type photosensitive resin composition of 1 to 20% by mass, particularly 3 to 12% by mass is preferable.

A solvent can be further added to the photosensitive composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing each of the above components (the photopolymerization initiator of the present invention and the polymerizable compound having an ethylenically unsaturated bond), for example, methyl ethyl ketone, methyl amyl. Ketones, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and other ketones; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol. Ether-based solvents such as dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; ethylene glycol monomethyl ether Cellosolve solvent such as ethylene glycol monoethyl ether; alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate and other ether ester solvents; benzene, toluene, xylene and other BTX solvents; hexane , Heptane, octane, cyclohexane and other aliphatic hydrocarbon solvents; terpine oil, D-limonene, pinene and other terpene hydrocarbon oils; mine Parasitic solvents such as Ruspirite, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.) and Solvesso # 100 (Exxon Chemical Co.); halogenated aliphatic carbonization such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane. Hydrogen-based solvent; halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol-based solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N -Methylpyrrolidone; dimethylsulfoxide; water and the like, and these solvents can be used as one kind or as 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 since the resist and the photopolymerization initiator have good compatibility in the photosensitive composition.

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

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; antanthrone compounds; perinone. Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; furnace method, channel method or thermal method Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; the above carbon black Prepared by coating or coating with an epoxy resin, the carbon black previously dispersed in a solvent with a resin to adsorb 20 to 200 mg / g of resin, the carbon black treated with an acidic or alkaline surface, the average Those having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and the total oxygen amount calculated from CO and CO ₂ in volatile matter at 950 ° C. is 9 mg or more per 100 m ² of surface area of carbon black; graphite , Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based , Ferrocyanide Phosphate ultramarine, navy blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black, amber and other organic or inorganic Pigments can be used. These pigments may be used alone or in combination of two or more.

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

  Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes. , Dyes such as cyanine dyes, and the like, and a plurality of these may be mixed and used.

  In the colored alkaline developable photosensitive composition of the present invention, the content of the coloring material is preferably 50 to 350 parts by mass, more preferably 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. It is 100 to 250 parts by mass.

The photosensitive composition of the present invention may 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, milori blue, calcium carbonate, Magnesium carbonate, cobalt-based, manganese-based, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicates, calcium silicates, aluminum hydroxide, platinum, Gold, silver, copper, etc. are mentioned.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by mass, more preferably 10 to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. It is 800 parts by mass. In addition, these inorganic compounds can use 1 type (s) or 2 or more types.

  These inorganic compounds are used, for example, as a filler, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, an ink repellent agent, and the like.

  A dispersant that disperses a colorant 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 such as BYK series manufactured by BYK Chemie can be used. In particular, a polymer dispersant comprising a polyester, polyether or polyurethane having a basic functional group, a nitrogen atom as a basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof. And those having an amine value of 1 to 100 mgKOH / g are preferably used.

  In the photosensitive composition of the present invention, another photopolymerization initiator can be used in combination with the photopolymerization initiator of the present invention. As the other photopolymerization initiator that can be used in combination, it is possible to use a conventionally known compound, for example, benzophenone, phenylbiphenyl ketone, 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-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-bu Tylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl)- s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine , Camphorquinone, N-1414, N-1717, N-1919, PZ-408 (made by ADEKA), IRGACUR 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), benzoyl peroxide, compounds represented by the following general formulas (V) to (VII), and the like. When used, the amount used is preferably not more than 1 mass times the amount used of the oxime ester compound of the present invention. These photopolymerization initiators can be used alone or in combination of two or more.

（式中、Ｒ¹及びＲ²は、上記一般式（Ｉ）中のＲ¹及びＲ²と同じであり、Ｒ³³は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基を表し、Ｒ³³で表される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、Ｙ³は、ハロゲン原子又はアルキル基を表し、ｎは０〜５の整数である。）

(Wherein, R ¹ and R ² are the same as R ¹ and R ² in the general formula (I), R ³³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon atoms 6 To an aryl group having 30 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, the alkyl part of the group represented by R ³³ may have a branched side chain, may be cyclic alkyl, and may be Y ³ Represents a halogen atom or an alkyl group, and n is an integer of 0 to 5.)

（式中、Ｒ¹及びＲ²は、上記一般式（Ｉ）中のＲ¹及びＲ²と同じであり、Ｒ³³は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基を表し、Ｒ³³で表される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、Ｙ³及びｎは上記一般式（V）と同じであり、Ｒ’¹及びＲ’²は、Ｒ¹と同じであり、Ｒ’³³はＲ³³と同じであり、Ｙ’³はＹ³と同じであり、Ｒ⁸はジオール残基又はジチオール残基を表し、Ｚ⁵は酸素原子又は硫黄原子を表す。）

(Wherein, R ¹ and R ² are the same as R ¹ and R ² in the general formula (I), R ³³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon atoms 6 To an aryl group having 30 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, the alkyl part of the group represented by R ³³ may have a branched side chain, may be cyclic alkyl, and may be Y ³ And n are the same as those in the general formula (V), R ′ ¹ and R ′ ² are the same as R ¹ , R ′ ³³ is the same as R ³³ , and Y ′ ³ is the same as Y ³ . And R ⁸ represents a diol residue or a dithiol residue, and Z ⁵ represents an oxygen atom or a sulfur atom.)

（式中、Ｒ¹及びＲ²は、上記一般式（Ｉ）中のＲ¹及びＲ²と同じであり、Ｒ³³は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基を表し、Ｒ³³で表される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、Ｙ³及びｎは、上記一般式（V）と同じであり、Ｚ⁶は酸素原子、硫黄原子又はセレン原子を表し、Ａは複素環基を表し、ｔは０〜５の整数であり、ｕは０又は１である。）

(Wherein, R ¹ and R ² are the same as R ¹ and R ² in the general formula (I), R ³³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon atoms 6 To an aryl group having 30 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, the alkyl part of the group represented by R ³³ may have a branched side chain, may be cyclic alkyl, and may be Y ³ And n are the same as those in the general formula (V), Z ⁶ represents an oxygen atom, a sulfur atom or a selenium atom, A represents a heterocyclic group, t is an integer of 0 to 5, and u is 0. Or 1.)

  In the photosensitive composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as a foaming agent, a leveling agent, a surface modifier, an antioxidant, an ultraviolet absorber, a dispersion aid, an anticoagulant, a catalyst, an effect accelerator, a crosslinking agent, a thickener, and the like 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 oxime ester compound of the present invention (provided that the above-mentioned other photopolymerization initiator, an ethylenically unsaturated group are contained). The amount of the compound having an alkali developability, the inorganic compound (filler), the coloring material, and the solvent, which may be used, is appropriately selected depending on the purpose of use and is not particularly limited, but preferably the above-mentioned ethylenic The total amount is 50 parts by mass or less with respect to 100 parts by mass of the polymerizable compound having a saturated bond.

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

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

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

  Examples of the above-mentioned surfactants include fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkylcarboxylates; anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates; higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

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

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolurea. Examples thereof include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group forming the alkyl ether include a methyl group, an ethyl group, and a butyl group, and they may be the same as or different from each other. Further, the non-alkyl etherified methylol group may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

  The method for forming a cured product of the present invention comprises a step of preparing a substrate, a step of applying the photosensitive composition of the present invention, an alkali developable photosensitive resin composition, or a colored alkali developable photosensitive resin composition to a substrate. And a step of irradiating an energy ray.

  Examples of the material of the substrate include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass such as soda glass and quartz glass; metal. Metals such as ruthenium; cellulose esters such as diacetyl cellulose, triacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose; polyamides; polycarbonates; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4 -Cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate Polyester such as; polystyrene; polyolefin such as polyethylene, polypropylene, polymethylpentene; acrylic resin such as polymethylmethacrylate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyetherimide; polyoxyethylene, norbornene resin, etc .; Is mentioned. Of these, the use of polyethylene terephthalate is preferable because it provides good adhesion between the cured product and the substrate. Examples of the shape of the base include a plate shape, a spherical shape, a fibrous shape, and a scaly shape. The base surface may be a flat surface or may have a three-dimensional structure such as a trench structure. The shape of the substrate used in the method for forming a cured product of the present invention is preferably plate-like, and the surface thereof is preferably flat.

The coating method used in the coating step is not particularly limited, for example, spin coater, roll coater, bar coater, die coater, curtain coater, various printing, using a known means such as dipping You can Alternatively, the method for forming a cured product of the present invention may be used to form the cured product on the first substrate and then transfer it to the second substrate.

  The energy ray light source used in the step of irradiating the energy ray is not particularly limited, but for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp. , Xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., with electromagnetic wave energy and electron beams and X-rays having wavelengths of 2000 angstroms to 7000 angstroms , High energy rays such as radiation can be used. Preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc., which emit light with a wavelength of 300 to 450 nm are used.

  Furthermore, by using laser light as the exposure light source, the laser direct writing method that directly forms an image from digital information from a computer without using a mask improves not only productivity but also resolution and positional accuracy. It is also useful because the laser light having a wavelength of 340 to 430 nm is preferably used, and an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser is preferably used. Various semiconductor lasers and YAG lasers that emit light in the visible to infrared region are also used. When using these lasers, sensitizing dyes that absorb in the visible to infrared region of interest are added. It can also be used by using a halftone mask.

  The photosensitive composition of the present invention comprises a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; a color filter in a color display liquid crystal display device such as a color television, a PC monitor, a personal digital assistant, a digital camera; Image sensor color filter; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photoresist for electronics; Electroplating resist; Etching resist; Dry film; Solder resist; resist for manufacturing color filters for various display applications or for forming structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; composition for encapsulating electrical and electronic components Thing; solder resist; magnetic recording material; micro mechanical parts Waveguides; Optical switches; Plating masks; Etching masks; Color test systems; Glass fiber cable coatings; Screen printing stencils; Materials for producing three-dimensional objects by stereolithography; Holographic recording materials; Image recording materials; Fine electronic circuit; Decolorization material; Decolorization material for image recording material; Decolorization material for image recording material using microcapsules; Photoresist material for printed wiring board; Photoresist material for UV and visible laser direct image system; It can be used for various applications such as a photoresist material or a protective film used for forming a dielectric layer in successive lamination of printed circuit boards, and the application is not particularly limited.

  The photosensitive composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive composition for simultaneously forming a protrusion and a spacer for a vertical alignment type liquid crystal display device.

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

  INDUSTRIAL APPLICABILITY The (colored) photosensitive composition of the present invention to which an ink repellent is added is useful as a partition wall forming resin composition for an inkjet system, and the composition is used for a color filter, and particularly when the profile angle is 50 ° or more. It is preferably used for a partition wall for an inkjet type color filter. As the ink repellent, a fluorine-containing surfactant and a composition containing a fluorine-containing surfactant are preferably used.

  The optical element is formed by a method in which a partition formed from the photosensitive composition of the present invention divides the transferred material, and droplets are applied to the recessed portions on the transferred material by the inkjet method to form an image area. Manufactured. At this time, it is preferable that the droplets contain a colorant and the image area is colored, and at least a pixel group formed of a plurality of colored areas and a partition wall separating each colored area of the pixel group are formed on the substrate. An optical element which has the above-described optical element and is manufactured by the above-described optical element manufacturing method is preferably used.

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

The protective film, the photosensitive composition for the insulating film,
(A) a carboxyl group-containing resin obtained by reacting a diol compound with polyvalent carboxylic acids, having a weight average molecular weight of 2,000 to 40,000 and an acid value of 50 to 200 mgKOH / g,
(B) an unsaturated compound containing at least one photopolymerizable ethylenically unsaturated bond in one molecule,
(C) epoxy compound, and (D) photopolymerization initiator of the present invention,
Is a resin composition containing as a main component.
In the photosensitive composition for the protective film and insulating film, the component (C) is 10 to 40 parts by weight and the component (D) is 0 based on 100 parts by weight of the total of the components (A) and (B). Those containing 0.01 to 2.0 parts by weight and the compound represented by the above general formula (I) as the photopolymerization initiator of the component (D) are preferable.

  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 support substrate, and the laminated body can be developed with an alkaline aqueous solution. The film thickness of 10 to 100 μm is preferable.

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

  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.

[Example 1] Compound No. 35 production

Compound No. To a solution of 107 (3.74 g, 10.0 mmol) dissolved in 20 ml of tetrahydrofuran was added 4-dimethylaminopyridine (0.61 g, 5.0 mmol) and carbonylimidazole (0.81 g, 5.0 mmol) at room temperature, The mixture was stirred at room temperature for 14 hours. After stirring, a saturated aqueous solution of ammonium chloride was added, the mixture was extracted with toluene, the solvent was distilled off by further reducing the pressure, and the obtained residue was subjected to silica gel column chromatography, and mixed solvent of ethyl acetate and n-hexane (volume ratio). Compound No. was obtained from the fraction of ethyl acetate: n-hexane = 1: 3). 35 was obtained.
(Analysis value)
(1) ¹ H-NMR (solvent: heavy benzene) (chemical shift: H number: multiplicity: splitting interval)
(7.93, 4H, d, 8.5Hz) (7.46, 4H, d, 8.5Hz) (7.07, 4H, d, 8.5Hz) (6.96, 4H, d, 8. 5Hz) (4.56, 4H, t, 4.6Hz) (4.26, 4H, t, 4.6Hz) (2.26, 6H, s) (2.25, 6H, s)
(2) IR (neat): 2959, 2934, 2892, 1778, 1750,
1662, 1585, 1493, 1455, 1404, 1367, 1268, 1231, 1175, 1081, 1037, 995, 940, 882, 831 cm ^-1
(3) ESI-MS m / z: 790.2 (M + NH ₄ ⁺ ).
(4) TG / TDA: 220 ° C (decomposition start temperature)
(5) UV (PGMEA): λmax = 328 nm (ε = 3.18 × 10 ⁴ ).
(6) Solubility (PGMEA):> 30 wt%

Example 2 Compound No. Production of Compound No. 19 To a solution of 91 (4.15 g, 10.0 mmol) dissolved in 25 ml of tetrahydrofuran was added 4-dimethylaminopyridine (0.61 g, 5.0 mmol) and carbonylimidazole (0.81 g, 5.0 mmol) at room temperature, The mixture was stirred at room temperature for 16 hours. After stirring, a saturated aqueous solution of ammonium chloride was added, the mixture was extracted with toluene, the solvent was distilled off by further reducing the pressure, and the obtained residue was subjected to silica gel column chromatography, and mixed solvent of ethyl acetate and n-hexane (volume ratio). Compound No. was obtained from the fraction of ethyl acetate: n-hexane = 2: 3). I got 19.

(Analysis value)
ESI-MS m / z: 874.2 (M + NH 4 +)

Example 3 Compound No. Production of Compound No. 47 4-dimethylaminopyridine (0.61 g, 5.0 mmol) and carbonylimidazole (0.81 g, 5.0 mmol) were added to a solution prepared by dissolving 117 (4.35 g, 10.0 mmol) in 25 ml of tetrahydrofuran at room temperature, The mixture was stirred at room temperature for 16 hours. After stirring, a saturated aqueous solution of ammonium chloride was added, the mixture was extracted with toluene, the solvent was distilled off by further reducing the pressure, and the obtained residue was subjected to silica gel column chromatography, and mixed solvent of ethyl acetate and n-hexane (volume ratio). Compound No. was obtained from the fraction of ethyl acetate: n-hexane = 2: 3). Got 47.

(Analysis value)
ESI-MS m / z: 914.2 (M + NH 4 +)

[Example 4] Production of composition A composition was compounded as shown in Table 1, and the composition of Example composition No. It was set to 1-10.

[Production Example 1]
Compositions were blended in the formulations shown in Table 2 to give Comparative Compositions 1 and 2.

[Evaluation Example 1] Solubility test Example composition No. 1 to 10 and Comparative Compositions 1 and 2 were evaluated for solubility in propylene glycol monomethyl ether acetate.
The case where more than 20 mass% of the composition was dissolved was designated as ++, the case where 20 to 17 mass% was dissolved was defined as +, and the case where less than 17 mass% was dissolved was defined as −. The results are shown in Table 3.

  From the results in Table 1, it was found that Evaluation Examples 1-1 to 1-10 exhibited higher solubility than Comparative Examples 1 and 2. Among them, it was found that Evaluation Examples 1-3, 1-6, 1-9 and 1-10 exhibited particularly high solubility.

[Example 5] Production of alkali-developable photosensitive resin composition SPC-1000 (acrylic resin; Showa Denko KK) 55 g, Aronix M-450 (polyfunctional acrylate; Toa Gosei KK) 13 g, KBE-403 (silane 0.57 g of coupling agent; manufactured by Shin-Etsu Silicone Co., Ltd., 3.2 g of a 1% cyclohexanone solution of FZ-2122 (surfactant; manufactured by Nippon Unicar Co., Ltd.) and 28 g of propylene glycol-1-monomethyl ether-2-acetate are mixed. , 15 g from the mixed solution, and the composition No. 1 to 10 0.20 g of each was added and stirred to obtain the alkali-developable photosensitive resin composition No. 1-10 were obtained.

[Production Example 2] Production of comparative alkaline developable photosensitive resin composition SPC-1000 (acrylic resin; Showa Denko KK) 55 g, Aronix M-450 (multifunctional acrylate; Toa Gosei KK) 13 g, KBE-403 ( 0.57 g of silane coupling agent; manufactured by Shin-Etsu Silicone Co., Ltd., 3.2 g of a 1% cyclohexanone solution of FZ-2122 (surfactant; manufactured by Nippon Unicar Co., Ltd.) and 28 g of propylene glycol-1-monomethyl ether-2-acetate. Then, 15 g of the mixture was weighed out, and 0.20 g of Comparative Example Composition 1 or 2 was added thereto, respectively, and stirred to obtain Comparative Alkali Developable Photosensitive Resin Compositions 1 and 2.

[Example 6] Production of cured product of Example Alkali developable photosensitive resin composition No. Each of 1 to 10 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 thoroughly washed with water, and post-baked at 230 ° C. for 30 minutes in an oven to fix the pattern. 1-10 were obtained.

[Production Example 3] Production of Comparative Cured Product Comparative alkali-developable photosensitive resin compositions 1 and 2 were each spin-coated on a glass substrate, prebaked at 90 ° C. for 90 seconds using a hot plate, and subjected to high pressure as a light source. It was exposed through a mask using a mercury lamp. After development using a 2.5% by mass aqueous solution of sodium carbonate as a developing solution, it was thoroughly washed with water, and post-baked at 230 ° C. for 30 minutes in an oven to fix the pattern, thereby obtaining comparative cured products 1 and 2. It was

[Evaluation Example 2] Radiation sensitivity evaluation Cured product No. The cross-sectional shapes of 1 to 10 and comparative cured products 1 and 2 were observed by SEM.
When the width of the lower part of the cured product is larger than the width of the upper part of the cured product, the cross section is +, and when the width of the lower part of the cured product is the same or smaller than the width of the upper part of the cured product, −. did. The results are shown in Table 4.

  From the results of Table 4, it was found that all of Evaluation Examples 2-1 to 2-10 had a cross-sectional shape in which the width of the lower part of the cured product was larger than the width of the upper part of the cured product. On the other hand, in Comparative Example 3 and Comparative Example 4, it was found that the width of the lower part of the cured product was the same or smaller than the width of the upper part of the cured product. When the width of the lower part of the cured product is larger than the width of the upper part of the cured product, it is known that the collapse or peeling of the cured product is less likely to occur, so the present invention provides a cured product having a desired shape. It has been found that the composition is suitable for forming.

Claims (12)

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

(In the formula, ^{R 1} represents independently an alkyl group having carbon atom number of 1 to 20, an aryl group of carbon atom number of 6 to 30, an arylalkyl group or CN having 7 to 30 carbon atoms,
Hydrogen atom of the substituents represented by R ¹ in a further ^{O R 21, COR 21, SR} 21, may have been substituted with C androgenic atom, or COOR ^21,
R ^{2 1} represents an alkyl group of water atom or 1 to 20 carbon atoms,
R ^2's each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,
The hydrogen atom of the substituent represented by R ² may be further substituted with a halogen atom,
Alkylene moiety of the substituents represented by R ^{1, R 2} and R ^{2 1} is, -O -, - S -, - COO -, - OCO- or -NR ²⁴ - in is interrupted more 1-5 times In some cases,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. ,
Alkyl moiety of the substituents represented by R ^1, R ² and R ^{2 1} are there may be branched side chain, may be cyclic alkyl,
Z ¹ is a bond and represents a single bond , —O— , —S— , —OCO— or —COO—,
Z ² is a bond, represents alkanediyl group single bond or a carbon atom number of 1 to 20,
The alkylene portion of the bond represented by Z ² may have a branched side chain, and may be cyclic alkylene.
X represents a bond represented by the following chemical formula (IA) or (IB). )

(In formulas (IA) and (IB), * represents a bond.) R ¹ Each independently represents an alkyl group having 1 to 20 carbon atoms,
R ^Two Each independently represents an alkyl group having 1 to 20 carbon atoms,
R ^Two The alkylene portion of the alkyl group represented by may be interrupted 1 to 5 times by -O-,
Z ¹ Is a single bond, -O-, -OCO-, or -COO-, The compound of Claim 1. The compound according to claim 1 or 2, wherein X is a bond represented by the chemical formula (IA). A photopolymerization initiator containing the compound according to claim 1. (A) The compound according to any one of claims 1 to 3 ,
(B) A composition containing a compound represented by the following general formula (II).

^(Wherein, is R ^1, R 2, ^{Z 1} and ^{Z 2 R} 1 in the general formula ^(I), R 2, the same meaning as ^{Z 1} and ^{Z 2, Z a} represents OH or COOH.) A photopolymerization initiator containing the composition according to claim 5 . A photosensitive composition comprising the photopolymerization initiator according to claim 4 or 6 containing a polymerizable compound having an ethylenically unsaturated bond. An alkali-developable photosensitive resin composition comprising the photosensitive composition according to claim 7 and a compound having an alkali developability which may have an ethylenically unsaturated group. The alkali-developable photosensitive resin composition according to claim 8 , further comprising an inorganic compound. A colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition according to claim 8 or 9 further containing a coloring material. A step of preparing a substrate, the photosensitive composition according to claim 7 , the alkali developable photosensitive resin composition according to claim 8 or 9 , or the colored alkali developable photosensitive resin composition according to claim 10 . A method for forming a cured product, which comprises the steps of applying to a substrate and irradiating with energy rays. Curing by curing the photosensitive composition according to claim 7 , the alkali developable photosensitive resin composition according to claim 8 or 9 , or the colored alkali developable photosensitive resin composition according to claim 10. object.