JPWO2019013112A1 - Oxime ester compound and photopolymerization initiator containing the compound - Google Patents

Abstract

An oxime ester compound represented by the following general formula (I). (In the formula, at least three of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, and R13 are groups represented by the following general formula (II). At least one of R3, R6 and R11 is preferably a group represented by the general formula (II).)

Description

  The present invention provides a novel oxime ester compound useful as a photopolymerization initiator used in a photosensitive composition, a photopolymerization initiator containing the compound, and a photosensitizer containing the photopolymerization initiator and an ethylenically unsaturated compound. Sex composition.

  The photosensitive composition is a composition obtained by adding a photopolymerization initiator to an ethylenically unsaturated compound, and can be polymerized and cured by irradiation with energy rays (light). Therefore, a photocurable ink or a photosensitive printing plate is used. It is used for various photoresists.

  As a photopolymerization initiator used in the photosensitive composition, Patent Document 1 discloses an oxime ester photopolymerization initiator having a carbazole skeleton. Further, Patent Document 2 discloses a polymerization initiator having an oxime ester compound having a triarylamine skeleton. However, the oxime ester compounds described in Patent Documents 1 and 2 are not compatible with each other at a level capable of satisfying sensitivity, heat resistance (low sublimation property) and transparency (high brightness of color filter).

  Further, a colored alkali-developable photosensitive composition containing a colorant such as a color filter is required to have high sensitivity, and therefore the photopolymerization initiator in the resist needs to have a high concentration. However, the photopolymerization initiator having a high concentration of the photopolymerization initiator causes a residue due to deterioration of developability, contamination of a photomask or a heating furnace due to a sublimate, and a cured product being colored, resulting in poor brightness. Was there.

International Publication No. 2008/138732 International Publication No. 2017/033880

  Therefore, an object of the present invention is to provide a highly sensitive oxime ester compound useful as a photopolymerization initiator having a high transmittance in the visible light region and a photopolymerization initiator and a photosensitive composition using the compound, An object of the present invention is to provide a color filter having high brightness and a display device including the color filter.

  The present invention has solved the above problems by providing the following [1] to [9].

  [1] An oxime ester compound represented by the following general formula (I).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、及びＲ^１３は、それぞれ独立に、下記一般式（II）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、アミノ基、Ｒ^２１、ＯＲ^２１、ＳＲ^２１、ＮＲ^２２Ｒ^２３、ＣＯＲ^２１、ＳＯＲ^２１、ＳＯ_２Ｒ^２１又はＣＯＮＲ^２２Ｒ^２３を表し、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、及びＲ^１３のうち、少なくとも三つが下記一般式（II）で表される基であり、
Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立に、炭素原子数１〜２０の炭化水素基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ^２１、Ｒ^２２及びＲ^２３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は炭素原子数２〜２０複素環含有基で置換される場合があり、
Ｒ^２１、Ｒ^２２及びＲ^２３で表される基中のメチレン基は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^２４−、−ＮＲ^２４ＣＯ−、−Ｓ−、−ＣＳ−、−ＳＯ_２−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又はＣＳＯ−で置換される場合があり、
Ｒ^２４は、水素原子、炭素原子数１〜２０の炭化水素基を表し、
Ｘ^１は、不存在、直接結合、−ＣＯ−、−Ｏ−又は−Ｓ−を表す。）

(In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R < ⁷ >, R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R <^11> , R <^12> , and R <^13> are each independently the following. Group represented by formula (II), hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, amino group, R ²¹ , OR ²¹ , SR ²¹ , NR ²² R ²³ , COR ²¹ , SOR ²¹ , SO ₂ R ²¹ or CONR ²² R ²³ ,
At ^{least three of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are of the following general formula (II ) Is a group represented by
R ²¹ , R ²² and R ²³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
The hydrogen atom in the groups represented by R ²¹ , R ²² and R ²³ is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group. , A mercapto group, an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms may be substituted,
Methylene groups in the group represented by R ^{21, R 22} and ^{R 23} is -O -, - CO -, - COO -, - OCO -, - NR 24 -, - NR 24 CO -, - S -, - _{CS -, - SO 2 -,} - SCO -, - COS -, - OCS- or CSO- in may be substituted,
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X ¹ represents absent, a direct bond, —CO—, —O— or —S—. )

（式中、Ｒ^３１及びＲ^３２は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１〜２０の炭化水素基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ^３１及びＲ^３２で表される基中の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は炭素原子数２〜２０複素環含有基で置換される場合があり、
Ｒ^３１及びＲ^３２で表される基中のメチレン基は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^３３−、−ＮＲ^３３ＣＯ−、−Ｓ−、−ＣＳ−、−ＳＯ_２−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又はＣＳＯ−で置換される場合もあり、
Ｒ^３３は、水素原子、炭素原子数１〜２０の炭化水素基を表し、
ｎは０又は１を表し、＊は結合手を表す。）

(In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms. ,
The hydrogen atom in the group represented by R ³¹ and R ³² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, It may be substituted with an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
Methylene groups in the group represented by R ³¹ and ^{R 32} -O -, - CO -, - COO -, - OCO -, - NR 33 -, - NR 33 CO -, - S -, - CS-, _{-SO 2 -, - SCO -,} - COS -, - OCS- or CSO- in some cases be substituted,
R ³³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1, and * represents a bond. )

[2] The oxime ester compound according to [1], wherein at least one of R ³ , R ⁶ and R ^{11 in} the general formula (I) is a group represented by the general formula (II).

  [3] A photopolymerization initiator containing the oxime ester compound according to [1] or [2].

  [4] A photosensitive composition containing the photopolymerization initiator (A) according to [3] and an ethylenically unsaturated compound (B).

  [5] The photosensitive composition according to [4], which further contains a colorant (C).

  [6] An alkali developable photosensitive resin composition containing the photosensitive composition according to [4] or [5] and an alkali developable compound (D).

  [7] A cured product of the photosensitive composition according to [4] or [5] or the alkali developable photosensitive resin composition according to [6].

  [8] A display device containing the cured product according to [7].

  [9] A method for producing a cured product, which comprises a step of curing the photosensitive composition according to [4] or [5] or the alkali developable photosensitive resin composition according to [6] by light irradiation or heating.

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

The oxime ester compound of the present invention is a novel compound represented by the above general formula (I). The oxime ester compound has geometrical isomers due to the double bond of the oxime, but they do not distinguish them.
That is, in the present specification, the compound represented by the general formula (I) and the exemplified compound thereof represent one kind or a mixture of two or more kinds of these geometrical isomers and have a structure showing a specific isomer. It is not limited to.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{21 to} R ²⁴ in the general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, Alkenyl group having 2 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkylalkyl group having 4 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms and 7 to 20 carbon atoms Represents an arylalkyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. , 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like are preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable.

  Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienyl allyl and the like can be mentioned. Particularly, an alkenyl group having 1 to 10 carbon atoms is preferable.

  The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the saturated monocyclic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of saturated polycyclic compounds include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo [1.1.1] pentanyl.

  The cycloalkylalkyl group having 4 to 20 carbon atoms means a group in which a hydrogen atom of an alkyl group has 4 to 20 carbon atoms substituted with a cycloalkyl group. For example, cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and deca. Hydronaphthyl propyl etc. are mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms 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. Be done.

  The arylalkyl group having 7 to 30 carbon atoms means a group in which a hydrogen atom of the alkyl group has 7 to 30 carbon atoms substituted with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned.

  Among the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms, since it has high sensitivity as a photopolymerization initiator, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to carbon atoms. A cycloalkyl group having 10 carbon atoms, a cycloalkylalkyl group having 4 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms and an arylalkyl group having 7 to 15 carbon atoms are particularly preferable.

In the above general formula (I), a hydrogen atom in the heterocyclic ring-containing group represented by R ^{21 to} R ²³ having 2 to 20 carbon atoms and the group represented by R ^{21 to} R ²³ may be substituted. Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl. , Benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolydyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone -1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl and the like can be mentioned.

The methylene group in the groups represented by R ^{21 to} R ²³ in the general formula (I) is —O—, —CO—, —COO—, —OCO—, —NR ²⁴ —, or —NR ²⁴ CO. _{-, - S -, - CS} -, - SO 2 -, - SCO -, - COS -, - OCS- or might be replaced by CSO-, may be the substitution of one or more groups In the case of a group that can be continuously substituted, two or more consecutive oxygen atoms may be continuously substituted under the condition that oxygen atoms are not adjacent to each other.

  Among the heterocyclic ring-containing groups having 2 to 20 carbon atoms, the heterocyclic ring-containing group having 2 to 10 carbon atoms is particularly preferable because it has high sensitivity as a photopolymerization initiator.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{31 to} R ³³ in the general formula (II) is the number of carbon atoms represented by R ^{21 to} R ²⁴ in the general formula (I). The same thing as the hydrocarbon group of 1-20 is mentioned.

In the above general formula (II), a hydrogen atom in the heterocyclic ring-containing group represented by R ³¹ and R ³² and having 2 to 20 carbon atoms and the group represented by R ³¹ and R ³² may be substituted. Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms include the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{21 to} R ²³ in the general formula (I).

The methylene group in the groups represented by R ³¹ and R ³² in the general formula (II) is —O—, —CO—, —COO—, —OCO—, —NR ²⁴ —, or —NR ²⁴ CO. _{-, - S -, - CS} -, - SO 2 -, - SCO -, - COS -, - OCS- or might be replaced by CSO-, may be the substitution of one or more groups In the case of a group that can be continuously substituted, two or more consecutive oxygen atoms may be continuously substituted under the condition that oxygen atoms are not adjacent to each other.

  Examples of the halogen atom in the above general formulas (I) and (II) include fluorine, chlorine, bromine and iodine.

The oxime ester compound in which X ¹ in the general formula (I) is absent or is a direct bond is preferable because it is excellent in brightness when used as a photopolymerization initiator, and the oxime ester compound in which X ¹ is a direct bond is It is particularly preferable because it is more excellent in sensitivity in addition to brightness. The absence of X ¹ in the present invention means that there is no atom at the position of X ^{1 and} the oxime ester compound represented by the general formula (I) has a triphenolamine skeleton.

When R ^{1 to} R ¹³ are groups other than the general formula (II), R ^{1 to} R ¹³ are preferably a hydrogen atom or a cyano group, particularly a hydrogen atom, because the synthesis is easy.

An oxime ester compound in which at least one, preferably two, and more preferably all of R ³ , R ⁶ and R ^{11 in} the general formula (I) are groups represented by the general formula (II) is It is preferable because the yield is good and the purification is easy. When all of R ³ , R ⁶ and R ^{11 in} the general formula (I) are groups represented by the general formula (II), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ and R ⁸ , An oxime ester compound in which R ⁹ , R ¹⁰ , R ¹² and R ¹³ are hydrogen atoms is preferable because the synthesis is easy.

  In the general formula (II), a cured product using an oxime ester compound with n = 1 as the photopolymerization initiator (A) is preferable because it has excellent transparency and brightness.

In the above general formula (II), it is preferable that R ³¹ is an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 7 carbon atoms because the solubility in an organic solvent is high. R ³² is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, an ethyl group or a phenyl group because of high reactivity.

  Specific preferred examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compound No. 1-No. 261 is mentioned. However, the present invention is not limited to the following compounds.

  The oxime ester compound of the present invention represented by the general formula (I) is not particularly limited, but can be synthesized, for example, by the method shown below.

When n in the general formula (II) is 0, it can be synthesized by the following reaction scheme. Specifically, a ketone compound 1 is obtained by reacting a known nitrogen-containing compound with a known and commercially available acid chloride, and the obtained ketone compound 1 is reacted with hydroxylamine hydrochloride to give an oxime compound. Get one. Subsequently, the oxime compound 1 is reacted with an acid chloride in the presence of triethylamine (TEA) to obtain the oxime ester compound 1 of the present invention represented by the general formula (I).
The oxime compound and the oxime ester compound can also be produced by the method described in WO 2008/078678.

In the above reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ³¹ , R ³² and X ¹ is R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ or R of the general formula (I) and the general formula (II). ^{The same applies to 12} , R ¹³ , R ³¹ , R ^32, and X ¹ .

When n in the general formula (II) is 1, it can be produced by the following method according to the following reaction formula.
That is, ketone compound 2 is obtained by reacting a known nitrogen-containing compound with an acid chloride, and oxime compound 2 is obtained by reacting ketone compound 2 with isobutyl nitrite. Subsequently, the oxime compound 2 is reacted with an acid anhydride or an acid chloride to obtain the oxime ester compound 2 of the present invention represented by the general formula (I).

In the above reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ³¹ , R ³² and X ¹ is R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ or R of the general formula (I) and the general formula (II). ^{The same applies to 12} , R ¹³ , R ³¹ , R ^32, and X ¹ .

  INDUSTRIAL APPLICABILITY The novel oxime ester compound of the present invention described above is useful for medicines, agricultural chemicals, base generators, photopolymerization initiators, and the like, and among the photopolymerization initiators, radical polymerization initiators (photoradical polymerization initiators or thermal radicals) are particularly preferable. It is useful as a polymerization initiator). Further, the novel oxime ester compound of the present invention can be suitably used as a sensitizer.

  The photosensitive composition of the present invention contains the photopolymerization initiator (A) of the present invention and an ethylenically unsaturated compound (B), and as an optional component, a colorant (C), an alkali developable compound (D), It contains a combination of components such as an inorganic compound and a solvent.

The photopolymerization initiator (A) of the present invention contains at least one oxime ester compound of the present invention represented by the general formula (I), and can be used in combination with other photopolymerization initiators. The content of the oxime ester compound of the present invention in the photopolymerization initiator (A) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
Further, the photopolymerization initiator (A) of the present invention is useful as a photopolymerization initiator for the ethylenically unsaturated compound (B).

  Other photopolymerization initiators not belonging to the general formula (I) are not particularly limited as long as they generate a radical upon irradiation with light, and conventionally known compounds can be used. For example, oxime ester compounds Preferred examples include acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds, and titanocene compounds.

  Examples of the oxime ester-based compound include compounds having a group represented by the general formula (II). Since the photopolymerization initiator has good sensitivity, the photosensitive composition of the present invention can be used. It can be preferably used.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{31 to} R ³³ in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms described in the general formula (I). It is the same.

The group having 2 to 20 carbon atoms containing a heterocycle which may modify the group represented by R ³¹ and R ³² and R ³¹ or R ³² in the general formula (II) is represented by the general formula (I). It is the same as the group having 2 to 20 carbon atoms containing a heterocycle described in.

  Among the oxime ester compounds having a group represented by the above general formula (II), the compound represented by the following general formula (III) has particularly high sensitivity, and therefore can be used in the photosensitive composition of the present invention. preferable.

  Among the oxime ester compounds having a group represented by the above general formula (I), the compound represented by the following general formula (III) has particularly high sensitivity, and therefore can be used in the photosensitive composition of the present invention. preferable.

^(Wherein, R ^{31, R 32} and n are the same as ^{R 31, R 32} and n, respectively, in formula (II),
R ⁴¹ and R ⁴² each independently represent a direct bond, a hydrogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 7 to 20 carbon atoms. Represents an arylalkyl group or a group having 2 to 20 carbon atoms containing a heterocycle,
X ¹¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁴³ R ⁴⁴ , CO, NR ⁴⁵ or PR ⁴⁶ ,
X ¹² represents a non-bond, a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or CO, and R ^{43 to} R ⁴⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or The hydrogen atom in the group represented by R ^{43 to} R ^46, which represents a heterocyclic ring-containing group having 2 to 20 carbon atoms, is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group or methacryloyl. Group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, or a heterocycle-containing group in some cases, and the methylene groups in the groups represented by R ^{41 to} R ⁴⁶ do not have oxygen adjacent to each other. -O in conditions -, - CO -, - COO -, - OCO -, - S -, - SO 2 -, - SCO- or -COS- in some cases be substituted,
R ^{41 to} R ⁴⁶ may each independently form a ring together with either adjacent benzene ring,
a represents a number from 0 to 4,
b represents the number of 0-3. )

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ in the general formula (III) is a hydrocarbon group having 1 to 20 carbon atoms described in the general formula (I). It is the same as the group.

The heterocyclic ring-containing group having 2 to 20 carbon atoms, which is represented by R ^{41 to} R ⁴⁶ in the general formula (III), is the heterocyclic ring-containing carbon represented by the general formula (I). It is the same as the group having 2 to 20 atoms.

  Preferred oxime ester compounds represented by the above general formula (III) include, for example, compound No. A2-1 to No. A2-28 is mentioned. However, the polymerization initiator (A) used in the present invention is not limited by the following compounds.

In the general formula (III), when X ¹ is a sulfur atom and X ² is a non-bond, the compound No. A oxime ester compound having a diphenyl sulfide skeleton represented by A2-1 to A2-7, and a photosensitive composition having good sensitivity can be obtained by using the oxime ester compound of the present invention as a polymerization initiator in combination. Is preferred.

In the general formula (III), when X ¹ is NR ⁵⁵ and X ² is a direct bond, the compound No. It becomes an oxime ester compound having a carbazole skeleton represented by A2-8 to A2-28, which is particularly preferable in that a photosensitive composition having good sensitivity can be obtained.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone and 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one and the like can be mentioned.

  Examples of the benzyl compound include benzyl.

  Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. Be done.

  Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

Examples of the phosphine oxide compound include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the titanocene compound include bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium.

  Examples of commercially available radical initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka Arcules NCI-831, NCI-930 (above, manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE ORE. 01, IRGACURE OXE 02, IRGACURE 784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, manufactured by TRONLY); and the like.

  In the photosensitive composition of the present invention, the content of the photopolymerization initiator (A) is not particularly limited, but is preferably 1 to 70 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound (B). Parts, more preferably 1 to 50 parts by weight, most preferably 5 to 30 parts by weight.

  The ethylenically unsaturated compound (B) has an ethylenically unsaturated bond. The ethylenically unsaturated compound (B) is not particularly limited, and those conventionally used in photosensitive compositions can be used, and examples thereof include ethylene, propylene, butylene, isobutylene, vinyl chloride and vinylidene chloride. Unsaturated vinyl hydrocarbons such as 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 Polymeric mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends such as mono (meth) acrylate; hydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate or 1 Unsaturated polybasic acids such as polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups; (meth) acrylic acid-2-hydroxyethyl, (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 (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, 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, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, Unsaturated monobasic acids such as pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomer and polyhydric alcohols or polyhydric alcohols Esters of phenols; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydro Phthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-malanic anhydride 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, vinylphenol. , Vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether and other unsaturated aromatic compounds; methyl vinyl ketone and other unsaturated ketones; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidine, etc. 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; indene such as indene and 1-methylindene; 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 the polymer molecular chain such as (meth) acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanate Nurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of vinyl monomer having hydroxyl group and polyisocyanate compound, vinyl epoxy compound of vinyl monomer having hydroxyl group and polyepoxy compound.

  A commercial item can be used as said ethylenically unsaturated compound (B), for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (Nippon Kayaku Co., Ltd.) SPC-. 1000, SPC-3000 (manufactured by Showa Denko), Aronix M-140, M-215, M-350 (manufactured by Toagosei Co., Ltd.), NK ester A-DPHA-TMPT, A-DCP, A-HD-N, A-. 9300, TMPT, DCP, NPG, HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  Among these, a polymer mono (meth) acrylate having a carboxyl group and a hydroxyl group at both ends, a polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups, and an unsaturated monocarboxylic acid Esters of basic acid and polyhydric alcohol or polyhydric phenol are suitable for the alkali-developable photosensitive resin composition of the present invention.

  The ethylenically unsaturated compounds may be used alone or in admixture of two or more kinds, and when two or more kinds are used in admixture, they are previously copolymerized and used as a copolymer. May be.

  The photosensitive composition of the present invention may further contain a colorant (C) to give a colored photosensitive composition. Examples of the colorant (C) include pigments, dyes and natural pigments. These colorants (C) can be used alone or in admixture of two or more.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; antanthrone compounds; perinone. Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; 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 or coated with an epoxy resin, the carbon black previously dispersed in a solvent in a resin, and 20 ~ 200 mg / g of resin adsorbed, the above carbon black subjected to acidic or alkaline surface treatment, having an 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 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; chrome oxide green, milori 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 (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, 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. , Cyanine dyes, and the like, and these may be used as a mixture of two or more.

  In the photosensitive composition of the present invention, the content of the colorant (C) is preferably 10 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound (B). It is a mass part.

  The photosensitive composition of the present invention may further contain an alkali developable compound (D) to give an alkali developable photosensitive resin composition. What simultaneously contains the colorant (C) and the alkali developable compound (D) is also referred to as a colored alkali developable photosensitive resin composition.

  The alkali developable compound (D) is not particularly limited as long as it is soluble in an alkaline aqueous solution, and examples thereof include the resins described in JP-A 2004-264414.

As the alkali developable compound (D), a copolymer of acrylic acid ester, phenol novolac epoxy resin, cresol novolac epoxy resin, polyphenylmethane type epoxy resin having a polyfunctional epoxy group, epoxy acrylate resin, carboxyl group A polymer obtained by reacting an unsaturated monobasic acid on an epoxy group of an epoxy compound such as an epoxy compound represented by the following general formula (IV) and further reacting a polybasic acid anhydride on the resin is used. be able to.
The above-mentioned epoxy acrylate resin is a compound obtained by allowing (meth) acrylic acid to act on an epoxy compound, and examples thereof include Ripoxy SPC-2000, DICLIGHT UE-777 manufactured by DIC, and Yupica 4015 manufactured by Japan Yupica. Can be mentioned.
Among these compounds, an epoxy acrylate resin and a polymer having a carboxyl group are preferable.

The polymer having a carboxyl group is not particularly limited as long as it has a structural unit having a carboxyl group (hereinafter referred to as “structural unit (U1)”). The polymer having a carboxyl group, in addition to the structural unit (U1), a structural unit having a crosslinkable group such as methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group and isocyanate group (hereinafter, referred to as " It is preferable to have a structural unit (U2) ”) and a structural unit having a silyl group (hereinafter referred to as“ structural unit (U3) ”).
The polymer having a carboxyl group may have a structural unit other than the structural units (U1) to (U3) (hereinafter, referred to as "structural unit (U4)").

The structural unit (U1) is a structural unit derived from at least one compound (hereinafter, referred to as “compound (u1)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. Preferably.
Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids.
Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexa. Hydrophthalic acid etc. can be mentioned.
Examples of the dicarboxylic acid include maleic acid, fumaric acid and citraconic acid.
Examples of the above-mentioned dicarboxylic acid anhydrides include the above-mentioned dicarboxylic acid anhydrides.
Among these compounds, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride is preferred from the viewpoints of copolymerization reactivity and solubility of the resulting copolymer in a developing solution. Acids are particularly preferred.
The above-mentioned polymer having a carboxyl group may have one kind of structural unit (U1) derived from one kind of compound (u1), and two or more kinds derived from two or more kinds of compound (u1). You may have a structural unit (U1).

The structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter referred to as “compound (u2)”).
The compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an epoxy group include (meth) acrylic acid oxiranyl (cyclo) alkyl ester, α-alkylacrylic acid oxiranyl (cyclo) alkyl ester, and a glycidyl ether compound having a polymerizable unsaturated bond. Be done.
Examples of the polymerizable unsaturated compound having an oxetanyl group include (meth) acrylic acid ester having an oxetanyl group.

Specific examples of (meth) acrylic acid oxiranyl (cyclo) alkyl ester include, for example, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth). 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 3,4- Epoxy tricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate etc. are mentioned.
Specific examples of the α-alkyl acrylic acid oxiranyl (cyclo) alkyl ester include, for example, α-ethyl glyceride glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl glyceride glycidyl, and α-ethyl acrylic acid 6 , 7-epoxyheptyl and 3,4-epoxycyclohexyl α-ethyl acrylate.
Specific examples of the glycidyl ether compound having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.
Specific examples of the (meth) acrylic acid ester having an oxetanyl group include, for example, 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-(( (Meth) acryloyloxymethyl) -2-methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (Meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane and the like can be mentioned.
Among these compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo [5.2.1] are particularly preferable. .0 ^2.6 ] decyl methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyl Oxymethyl oxetane or 3-ethyl-3-methacryloyloxymethyl oxetane is preferable from the viewpoint of polymerizability.
The above-mentioned polymer having a carboxyl group may have one kind of structural unit (U2) derived from one kind of compound (u2), and two or more kinds derived from two or more kinds of compound (u2). You may have a structural unit (U2).

Among the structural units (U2), as the structural unit having a methacryloyl group or acryloyl group as the crosslinkable group, a structural unit having a (meth) acryloyloxy group can be preferably used.
The structural unit having a (meth) acryloyloxy group is obtained by reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a polymer. The structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U).

（式中、Ｒ^１０００及びＲ^１００１は、それぞれ独立に、水素原子又はメチル基を表し、
ｕは、１〜６の整数を表し、
Ｒ^１００２は、下記式（Ｕα）又は下記式（Ｕβ）で表される２価の基を表し、
＊は結合手を表す。）

(In the formula, R ¹⁰⁰⁰ and R ¹⁰⁰¹ each independently represent a hydrogen atom or a methyl group,
u represents an integer of 1 to 6,
R ¹⁰⁰² represents a divalent group represented by the following formula (Uα) or the following formula (Uβ),
* Represents a bond. )

（式中、Ｒ^１００３は、水素原子又はメチル基を表し
＊は、結合手を表す。）

(In the formula, R ¹⁰⁰³ represents a hydrogen atom or a methyl group, and * represents a bond.)

Regarding the structural unit represented by the above formula (U), for example, when a copolymer having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate, R in the formula (U) ¹⁰⁰² becomes the formula (Uα). When the copolymer having a carboxyl group is reacted with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, R ¹⁰⁰² in the formula (U) becomes the formula (Uβ).

  The above-mentioned reaction of the carboxyl group and the unsaturated compound such as (meth) acrylic acid ester having an epoxy group in the polymer is carried out in the presence of a suitable catalyst, if necessary, preferably a polymer containing a polymerization inhibitor. It is preferable to add the unsaturated compound having an epoxy group to the solution of (1) and stir for a predetermined time while heating. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 hours to 12 hours.

  In the structural unit ratio of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth) acryloyloxy group as a crosslinkable group is 10 mol% to 70 mol of all the structural units of the polymer having a carboxyl group. %, And more preferably 20 mol% to 50 mol%. When the ratio of the structural unit having a (meth) acryloyloxy group is within the above range, heat resistance and development defects during development are reduced, and development residue can be suppressed.

  The structural unit (U3) is preferably a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter referred to as “compound (u3)”).

Examples of the compound (u3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth). ) Acryloyloxypropyltriethoxysilane and the like can be mentioned.
When the polymer having a carboxyl group has the structural unit U3, it may have one type of structural unit (U3) derived from one type of compound (u3), and may have two or more types of compound (u3). It may have two or more types of structural units (U3) derived from it.

The structural unit (U4) is a structural unit other than (U1) to (U3), and is a polymerizable unsaturated compound other than (u1) to (u3) (hereinafter, referred to as “compound (u4)”). A structural unit derived from is preferable.
Examples of the compound (u4) include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, Examples thereof include (meth) acrylic acid esters having a 5-membered oxygen-containing heterocyclic ring or a 6-membered oxygen-containing heterocyclic ring, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds.
Specific examples of the alkyl (meth) acrylate include methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. Examples thereof include sec-butyl acid and t-butyl (meth) acrylate.
Specific examples of the (meth) acrylic acid cycloalkyl ester include, for example, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, and (meth) acrylic acid tricyclo [5.2.1.0 ^2,6]. ] decan-8-yl, and (meth) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6] decan-8-yloxy) ethyl and (meth) isobornyl acrylic acid.
Specific examples of the (meth) acrylic acid aryl ester include phenyl acrylate and the like.
Specific examples of the (meth) acrylic acid aralkyl ester include, for example, benzyl (meth) acrylate.
Specific examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate and diethyl fumarate.
Specific examples of the (meth) acrylic acid ester having a 5-membered oxygen-containing heterocyclic ring or a 6-membered oxygen-containing heterocyclic ring include, for example, (meth) acrylic acid tetrahydrofuran-2-yl and (meth) acrylic acid tetrahydropyran-2- And 2-methyltetrahydropyran-2-yl (meth) acrylate and the like.
Specific examples of the vinyl aromatic compound include styrene and α-methylstyrene.
Specific examples of the conjugated diene compound include 1,3-butadiene and isoprene.
Specific examples of the other polymerizable unsaturated compound include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.
Among the compounds (u4) mentioned above, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclomethacrylate [5.2.1.0 ^2,6] ] Decane-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate and 1,3-butadiene are preferred.
When the polymer having a carboxyl group has a structural unit (U4), it may have one type of structural unit (U4) derived from one type of compound (u4), and may have two or more types of compound (u4). ) May have two or more types of structural units (U4).

The polymer having a preferable carboxyl group in the present embodiment is synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) in the following ratios, respectively. You can
Further, by reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a structural unit derived from the compound (u1) in the obtained copolymer, a (meth) acryloyloxy group is obtained. It may have a structural unit having.

Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, further preferably 5 mol% to 15 mol%
Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%.
Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%
Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, further preferably 25 mol% to 50 mol%

  The polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing the compound (u1) to the compound (u4) in the above range has good coating properties. Since a high resolution can be achieved without impairing it, a cured film having a highly balanced physical property can be obtained even with a high-definition pattern, which is preferable.

The weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. By using a polymer having a carboxyl group having an Mw in this range, high resolution can be achieved without impairing good coating properties, so that the balance of properties can be adjusted to a high degree even with a high-definition pattern. The cured film can be provided.
In the present invention, the weight average molecular weight (Mw) refers to the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).

  The polymer having a carboxyl group can be produced by polymerizing a mixture of the above polymerizable unsaturated compounds, preferably in a suitable solvent, preferably in the presence of a radical polymerization initiator.

  Examples of the solvent used in the polymerization of the mixture of the polymerizable unsaturated compound, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl Examples thereof include ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol and 3-methoxybutanol. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and includes, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2. '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Examples thereof include azo compounds such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

  Among the above-mentioned polymers having a carboxyl group, the polymer described in JP-A-2005-234362, an epoxy group of an epoxy compound represented by the following general formula (VI), an unsaturated monobasic acid is allowed to act, and further Polymers obtained by reacting polybasic acid anhydrides are preferred.

As the alkali developable compound (D), a copolymer of acrylic acid ester, phenol and / or cresol novolac epoxy resin, polyphenylmethane type epoxy resin having a polyfunctional epoxy group, epoxy acrylate resin, the following general A resin obtained by causing an unsaturated monobasic acid to act on an epoxy group of an epoxy compound such as the epoxy compound represented by the formula (III) and further causing a polybasic acid anhydride to act on the epoxy group can be used. The epoxy acrylate resin referred to here is a compound obtained by allowing (meth) acrylic acid to act on the above epoxy compound, and examples thereof include Ripoxy SPC-2000, DICLIGHT UE-777 manufactured by DIC, and Yupica Japan. Yupica 4015 and the like can be mentioned.
Among these, an epoxy acrylate resin and a resin obtained by causing an unsaturated monobasic acid to act on the epoxy group of the epoxy compound represented by the following general formula (IV) and further causing a polybasic acid anhydride to act on the epoxy group Is preferred.
Further, the compound having an alkali developability which may have an ethylenically unsaturated bond preferably contains an unsaturated group in an amount of 0.2 to 1.0 equivalent.

（式中、Ｘ^２１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−、−ＳＯ−₂、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は下記〔化３６〕、〔化３７〕若しくは〔化３８〕で表される基を表し、上記アルキリデン基はハロゲン原子で置換される場合もあり、Ｒ^５１、及びＲ^５２は、それぞれ独立に、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換される場合もあり、
Ｒ^５１、及びＲ^５２がそれぞれ複数存在する場合は、同一の場合も異なる場合もあり、
ｃは、０〜４の整数であり、
ｄは、０〜４の整数であり、
ｍは０〜１０の整数であり、
ｍが０でない場合に存在する光学異性体は、どの異性体でもよい。）

^{(Wherein, X 21} is a direct bond, methylene, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O -, - S -, - SO- 2, -SS-, -SO-, -CO-, -OCO- or a group represented by the following [Chemical Formula 36], [Chemical Formula 37] or [Chemical Formula 38], wherein the alkylidene group is substituted with a halogen atom. In addition, R ⁵¹ and R ⁵² each independently represent 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,
When a plurality of R ⁵¹ and R ⁵² are present, they may be the same or different,
c is an integer of 0 to 4,
d is an integer of 0 to 4,
m is an integer of 0-10,
The optical isomer present when m is not 0 may be any isomer. )

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

(In the formula, * represents a bond.)

(In the formula, Y ² and Z ² 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 aryloxy 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. The methylene group in the group represented by Y ² which represents a ring group or a halogen atom may be substituted with an unsaturated bond, —O— or —S—, and Z ² is the same as adjacent Z ² groups. May form a ring with, f represents an integer of 0-4, g represents an integer of 0-8, h represents an integer of 0-4, i represents an integer of 0-4, The total number of h and i is an integer of 2 to 4, and * represents a bond)

  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.

  Examples of the polybasic acid anhydride to be acted after acting the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic acid Acid anhydride, pyromellitic acid anhydride, 2,2'-3,3'-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhymic acid anhydride and the like.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to 1 epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 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.
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 (A) and an ethylenically unsaturated compound (B) as essential components. And an alkali developable compound (D), and as an optional component, a combination of components such as an inorganic compound and a solvent. Among the alkali-developable photosensitive resin compositions of the present invention, those containing a colorant (C) are also referred to as the colored alkali-developable photosensitive resin composition of the present invention.
The alkali developable compound (D) may be used alone or in combination of two or more.
When the alkali developable compound (D) has an ethylenically unsaturated bond, the alkali developable compound (D) may be included in the category of the ethylenically unsaturated compound (B). When the alkali developable compound (D) is also an ethylenically unsaturated compound (B), the composition containing the alkali developable compound (D) is a photosensitive composition, and the alkali developable photosensitive resin composition It is also a thing.

  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 combined with a single 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 the 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 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-nonyl phenyl glycidyl ether , Benzyl glycidyl ether, p-cumyl phenyl 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 above compound No. A2, No. A3 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 is obtained. It 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-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyl) Oxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane and the like can be used.
In addition, 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; 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 Type epoxy compounds and the like can also be used.

  In particular, when the photosensitive composition of the present invention is used as an alkali-developable photosensitive resin composition, the content of the compound having an alkali developability which may have an ethylenically unsaturated bond is determined by the alkali development of the present invention. In the photosensitive resin composition of the mold, 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. As the solvent, a solvent that can dissolve or disperse the above-mentioned components (photopolymerization initiator (A), ethylenically unsaturated compound (B), etc.) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc. Ether solvents; 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, ethylene glycol mono Cellosolve solvent such as ethyl 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- Ether ester solvents such as 1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, xylene; hexane, heptane, Aliphatic hydrocarbon solvents such as octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffinic solvent; halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol solvent; aniline Triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide (DMAc); N-methylpyrrolidone; dimethylsulfoxide; water, etc. Alternatively, they can be used 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 and cyclohexanone, have good compatibility between the resist and the photopolymerization initiator (A) in the photosensitive composition. Therefore, it is preferable.

  Further, the photosensitive composition of the present invention may contain p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, an inorganic compound, a latent additive, an organic polymer, a chain transfer agent, a sensitizer, if necessary. , Surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors, plasticizers, adhesion promoters, fillers, defoamers, leveling agents, surface modifiers, antioxidants, ultraviolet absorbers, dispersion aids Conventional additives such as an anti-agglomeration agent, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.

  A dispersant for dispersing the colorant (C) and / or the 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 colorant (C) or the inorganic compound, and a commercially available dispersant such as BYK series manufactured by Big Chemie Japan can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen functional atom having a nitrogen atom, 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.

  The latent additives are represented by the following general formulas (A) to (C).

（式中、環Ａ^１は、六員環の脂環、芳香環又は複素環であり、Ｒ^８１、Ｒ^８２、Ｒ^８３、Ｒ^８４及びＲ^８５は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又は−Ｏ−Ｒ^６６を表し、
Ｒ^８１、Ｒ^８２、Ｒ^８３、Ｒ^８４及びＲ^８５のうち少なくとも一つは水素原子でなく、
Ｒ^８６は、炭素原子数１〜２０のアルキル基、炭素原子数２〜２０のアルケニル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又はトリアルキルシリル基を表す。）

(In the formula, ring A ¹ is a 6-membered alicyclic ring, aromatic ring or heterocyclic ring, and R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are a hydrogen atom, a halogen atom, a cyano group or a hydroxyl group. , Nitro group, carboxyl group, optionally substituted alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, number of carbon atoms 2 to 20 heterocyclic ring-containing groups or -OR ⁶⁶ ,
At least one of R ⁸¹ , R ⁸² , R ⁸³ , R ^84, and R ⁸⁵ is not a hydrogen atom,
R ⁸⁶ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 2 to 2 carbon atoms. 20 represents a heterocyclic ring-containing group or a trialkylsilyl group. )

（式中、環Ａ^１及びＲ^９１は、上記一般式（Ａ）と同じであり、
Ｘ^７は、下記一般式（１）で表される基であり、Ｒ^９２、Ｒ^９３、Ｒ^９４及びＲ^９５は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、Ｒ^９２、Ｒ^９３、Ｒ^９４及びＲ^９５のうち少なくとも一つは水素原子でない。）

(In the formula, rings A ¹ and R ⁹¹ are the same as those in the general formula (A),
X ⁷ is a group represented by the following general formula (1), and R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group or a substituent. An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms, which may have At least one of R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ is not a hydrogen atom. )

（上記一般式（１）中、Ｘ^８は、−ＣＲ^９７Ｒ^９８−、−ＮＲ^９９−、二価の炭素原子数１〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環基、又は、下記〔化４２〕〜〔化４４〕で表されるいずれかの置換基を表し、
該脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−、或いは酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置換される場合があり、
Ｒ^９７及びＲ^９８は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｚ^５及びＺ^６は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、＞ＣＯ、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−又は＞ＮＲ^１００を表し、Ｒ^９９及びＲ^１００は、水素原子、置換基を有していてもよい炭素原子数１〜３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６〜３５の芳香族炭化水素基又は置換基を有していてもよい炭素原子数２〜３５の複素環基を表し、＊は結合手を表す。）

(In the general formula (1), X ⁸ is —CR ⁹⁷ R ⁹⁸ —, —NR ⁹⁹ —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an aromatic group having 6 to 35 carbon atoms. A hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, or any of the substituents represented by the following [Chemical Formula 42] to [Chemical Formula 44],
The methylene group in the aliphatic hydrocarbon group is -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a bond obtained by combining these without adjoining oxygen atoms. May be substituted with a group,
R ⁹⁷ and R ⁹⁸ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and Z ⁵ and Z ⁶ are each each independently a direct bond, -O -, - S -, > CO, -CO-O -, - O-CO -, - SO 2 -, - SS -, - SO- ^or> represents ^{NR 100,} R ⁹⁹ and R ¹⁰⁰ are each a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent. It represents a hydrogen group or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and * represents a bond. )

（上記式中、Ｒ^１０１は水素原子、置換基を有していてもよいフェニル基、又は炭素原子数３〜１０のシクロアルキル基を表し、Ｒ^１０２は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有していてもよく、ｆは０〜５の整数であり、＊は結合手を表し、＊は結合手を表す。）

(In the above formula, R ¹⁰¹ represents a hydrogen atom, an optionally substituted phenyl group, or a cycloalkyl group having 3 to 10 carbon atoms, and R ¹⁰² represents an alkyl group having 1 to 10 carbon atoms, It represents an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the above alkyl group, alkoxy group and alkenyl group may have a substituent, and f is 0 to 5 Is an integer of, * represents a bond, and * represents a bond.)

（式中、＊は結合手を表す。）

(In the formula, * represents a bond.)

（上記式中、Ｒ^１０３及びＲ^１０４は、それぞれ独立に、置換基を有していてもよい炭素原子数１〜１０のアルキル基、置換基を有していてもよい炭素原子数６〜２０のアリール基、置換基を有していてもよい炭素原子数６〜２０のアリールオキシ基、置換基を有していてもよい炭素原子数６〜２０のアリールチオ基、置換基を有していてもよい炭素原子数６〜２０のアリールアルケニル基、置換基を有していてもよい炭素原子数７〜２０のアリールアルキル基、置換基を有していてもよい炭素原子数２〜２０の複素環基又はハロゲン原子を表し、該アルキル基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｒ^１０３は、隣接するＲ^１０３同士で環を形成していてもよく、ｂは０〜４の数を表し、ｃは０〜８の数を表し、ｇは０〜４の数を表し、ｈは０〜４の数を表し、ｇとｈの数の合計は２〜４である。）

(In the above formula, R ¹⁰³ and R ¹⁰⁴ are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a C 6 to 20 carbon atom which may have a substituent. , An aryloxy group having 6 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, and a substituent An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroalkyl group having 2 to 20 carbon atoms which may have a substituent. It represents a ring group or a halogen atom, and the methylene group in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and R ¹⁰³ is a ring formed between adjacent R ^103. B may represent a number from 0 to 4, c represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, and g and The total number of h is 2 to 4.)

（式中、ｋ＝２〜６であり、Ｘ^９は、ｋ＝２のとき上記一般式（２）で表される基であり、ｋ＝３のとき下記一般式（３）で表される基であり、ｋ＝４のとき下記一般式（４）で表される基であり、ｋ＝５のとき下記一般式（５）であり、ｋ＝６のとき下記一般式（６）であり、Ｒ^１１１、Ｒ^１１２、Ｒ^１１３及びＲ^１１４は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、Ｒ^１１１、Ｒ^１１２、Ｒ^１１３及びＲ^１１４のうち少なくとも一つは水素原子でなく、環Ａ^１及びＲ^８６は、上記一般式（Ａ）と同じである。）

(In the formula, k = 2 to 6, and X ⁹ is a group represented by the general formula (2) when k = 2, and represented by the following general formula (3) when k = 3. A group represented by the following general formula (4) when k = 4, a general formula (5) below when k = 5, and a general formula (6) below when k = 6 , R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, It represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, and at least one of R ¹¹¹ , R ¹¹² , R ¹¹³ and R ^114. Is not a hydrogen atom, and rings A ¹ and R ⁸⁶ are the same as those in the above general formula (A).)

（上記一般式（２）中、Ｙ^１１は、三価の炭素原子数３〜３５の脂肪族炭化水素基、炭素原子数３〜３５の脂環族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環基を表し、Ｚ^１１、Ｚ^１２及びＺ^１３は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、＞ＣＯ、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ_２−、−ＳＳ−、−ＳＯ−、−ＮＲ^１２１−、−ＰＲ^１２１−又は置換基を有していてもよい炭素原子数１〜３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６〜３５の芳香族炭化水素基又は置換基を有していてもよい炭素原子数２〜３５の複素環基を表し、
Ｒ^１２１は、水素原子、置換基を有していてもよい炭素原子数１〜３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６〜３５の芳香族炭化水素基又は置換基を有していてもよい炭素原子数２〜３５の複素環基を表し、該脂肪族炭化水素基中のメチレン基は、炭素一炭素二重結合、−Ｏ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−又は−ＳＯ_２−で置換される場合もある。）

(In the above general formula (2), Y ¹¹ is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms. It represents an aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, and Z ¹¹ , Z ¹² and Z ¹³ each independently represent a direct bond, —O—, —S—,> CO, —CO—. _{O -, - O-CO -} , - SO 2 -, - SS -, - SO -, - NR 121 -, - PR 121 - or which may have a substituent aliphatic carbon atoms 1 to 35 A hydrocarbon group, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent,
R ¹²¹ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent. Or represents a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and the methylene group in the aliphatic hydrocarbon group is a carbon-carbon double bond, -O-, -CO-, -O-CO -, - there when substituted at - CO-O-or -SO _2. )

（上記一般式（３）中、Ｙ^１２は、炭素原子、又は、四価の炭素原子数１〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環基を表し、該脂肪族炭化水素基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置換される場合もあり、Ｚ^１１〜Ｚ^１４は、それぞれ独立に、上記一般式（２）におけるＺ^１１〜Ｚ^１３で表される基と同じ範囲の基である。）

(In the above general formula (3), Y ¹² is a carbon atom, or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or the number of carbon atoms. 2 to 35 heterocyclic groups, wherein the methylene group in the aliphatic hydrocarbon group is substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-. Also, Z ^{11 to} Z ¹⁴ are each independently the same range as the group represented by Z ^{11 to} Z ¹³ in the general formula (2).)

（上記一般式（４）中、Ｙ^１３は、五価の炭素原子数２〜３５の脂肪族炭化水素基、炭素原子数６〜３０の芳香族炭化水素基又は炭素原子数２〜３０の複素環基を表し、該脂肪族炭化水素基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で中断されていてもよく、Ｚ^１１〜Ｚ^１５は、それぞれ独立に、上記一般式（２）におけるＺ^１１〜Ｚ^１３で表される基と同じ範囲の基である。）

(In the general formula (4), Y ¹³ is a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a complex having 2 to 30 carbon atoms. Represents a cyclic group, the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ^{11 to} Z ¹⁵ are , Each of which is independently the same group as the group represented by Z ^{11 to} Z ¹³ in the general formula (2).)

（上記一般式（５）中、Ｙ^１４は、六価の炭素原子数２〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基又は炭素原子数２〜３５の複素環基を表し、該脂肪族炭化水素基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で中断されていてもよく、Ｚ¹¹〜Ｚ¹⁶は、それぞれ独立に、上記一般式（２）におけるＺ^１１〜Ｚ^１３で表される基と同じ範囲の基である。）

(In the general formula (5), Y ¹⁴ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a complex having 2 to 35 carbon atoms. Represents a cyclic group, the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ^{11 to} Z ¹⁶ are , Each of which is independently the same group as the group represented by Z ^{11 to} Z ¹³ in the general formula (2).)

By using the above organic polymer [excluding the ethylenically unsaturated compound (B)], the properties of the cured product can be improved. 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.
When the organic polymer is used, the amount thereof is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

  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-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis Mercapto compounds such as (3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid Iodinated alkyl compounds such as trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthio Propionate, 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, an aliphatic polyfunctional thiol compound 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 fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher-grade surfactants. Cationic surfactants such as amine 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-based interfaces Surfactants such as activators 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, an isocyanate group, an acryloyl group, such as KBE-9007, KBM-5103, KBM-502, and KBE-403. A silane coupling agent having a methacryloyl group or an epoxy group is preferably used.

Examples of the melamine compound include (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea, and other active methylol groups (CH ₂ OH groups) in nitrogen compounds. 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, 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, resulting in the formation of an oligomer component.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyl etherified melamine such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

  As the leveling agent, an existing leveling agent can be used as long as it has a leveling effect, and among them, a silicone type leveling agent and a fluorine type leveling agent can be particularly preferably used.

  As the above-mentioned silicone leveling agent, a commercially available silicone leveling agent can be used, and examples thereof include BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-. 322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720 (above, manufactured by Big Chemie Japan); ACFS180, ACFS360. S20 (above, manufactured by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (above, Kyoeisha Chemical Co., Ltd.); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (all manufactured by Shin-Etsu Chemical Co., Ltd.); LP-7001, LP-7002, 8032ADDITIVE, 57ADDITIVE, L-7604, FZ-2110, FZ-. Commercial products such as 2105, 67ADDITIVE, 8618ADDITIVE, 3ADDITIVE, 56ADDITIVE (above, manufactured by Toray Dow Corning) can be used.

  As the fluorine-based leveling agent, a commercially available fluorine-based leveling agent can be used, for example, OPTOOL DSX, OPTOOL DAC-HP (above, manufactured by Daikin Industries); Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-611, Surflon S-651, Surflon S-386 (above, manufactured by AGC Seimi Chemical); BYK-340 (manufactured by Big Chemie Japan); AC110a, AC100a (above, manufactured by AlginChemie); MegaFac F-114, MegaFac F-410, MegaFac F-444, MegaFac EXPTP-2066, MegaFac F-430, MegaFac F-472SF, MegaFac F-477, MegaFac F-552, MegaFac F-553, MegaFac F-554, MegaFac F-555, MegaFac R-94, MegaFac RS-72-K, MegaFac RS-75, MegaFac F-556, MegaFac EXPTF-1367, MegaFac EXPTF-1437, MegaFac F-558, Megafac EXPTF-1537 (above, manufactured by DIC); FC-4430, FC-4432 (above, manufactured by Sumitomo 3M); footgent 100, footgent 100C, footgent 110, footgent 150, footgent 150CH. , Footergent AK, Footergent 501, Footergent 250, Footergent 251, Footergent 222F, Footergent 208G, Footergent 300, Footergent 310, Footergent 400SW (above, manufactured by Neos); PF-136A, PF -156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, PF-3320 (above, manufactured by Kitamura Chemical Industry Co., Ltd.) You can

  In the photosensitive composition of the present invention, the polymerization initiator (A), the ethylenically unsaturated compound (B), the colorant (C), the alkali developable compound (D), the solvent, the inorganic compound and the organic polymer are excluded. The amount of the component used is appropriately selected depending on the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the ethylenically unsaturated compound (B).

  The photosensitive composition, alkali-developable photosensitive resin composition or cured product of the present invention is a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; a display device (color television, PC monitor, portable information terminal, Color filters in liquid crystal display devices for color display of digital cameras, etc .; Color filters for CCD image sensors; Electrode materials for plasma display panels; Powder coatings; Printing inks; Printing plates; Adhesives; Dental compositions; Gel coats; Electronics Engineering photoresists; Electroplating resists; Etching resists; Dry films; Solder resists; Resists for forming various display device structures; Compositions for encapsulating electrical and electronic components; Solder resists; Magnetic recording materials Micromechanical parts; Waveguides; Optical switches; Masks for plating; Etching masks; Color test systems; Fiberglass cable coatings; Stencils for screen printing; Materials for producing three-dimensional objects by stereolithography; Materials for holographic recording Image recording materials; fine electronic circuits; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; UV and visible laser direct image systems The photoresist material 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 or the alkali-developable photosensitive resin 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. Particularly, it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display device.

  The method for curing the photosensitive composition or the alkali-developable photosensitive resin composition of the present invention will be described in detail below.

  The photosensitive composition or the alkali-developable photosensitive resin composition of the present invention is a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, known means such as dipping, soda glass, quartz glass. It can be applied on a supporting substrate such as a semiconductor substrate, metal, paper or plastic. In addition, it is possible to apply it once to a supporting substrate such as a film and then transfer it to another supporting substrate, and the application method thereof is not limited.

  In addition, as a light source of energy rays used when curing the photosensitive composition alkali-developable photosensitive resin composition of the present invention, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, mercury Electromagnetic energy and electron beams with wavelengths of 2000 Å to 7000 Å obtained from steam arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc. , High-energy rays such as X-rays and radiation can be used, but preferably ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc., which emit light with a wavelength of 300 to 450 nm. Be done.

  Furthermore, by using laser light as the exposure light source, the laser direct writing method, which 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 is preferably light having a wavelength of 340 to 430 nm, and excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser. 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.

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

  INDUSTRIAL APPLICABILITY The 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 an inkjet system having a profile angle of 50 ° or more. It is preferably used for partition walls for color filters. As the ink repellent agent, a fluorosurfactant and a composition comprising a fluorosurfactant are preferably used.

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

  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.

[Examples 1-1 to 1-3] Compound No. Manufacturing 1

[Example 1-1] Production of intermediate 1A (ketone compound) After charging triphenylamine (3.3 g) and dichloroethane (15 g) in a four-necked flask, aluminum chloride (5.8 g) under ice cooling, Acetyl chloride (3.3 g) was added. After stirring at room temperature for 3 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with a 5% aqueous HCl solution and further washed four times with water. The product layer was desolvated and then purified by a silica gel column (hexane / ethyl acetate = 65/35) to obtain Intermediate 1A (2.6 g: yield 52%).

[Example 1-2] Production of intermediate 1B (oxime compound) A four-necked flask was charged with intermediate 1A (2.6 g), ethanol (24 g), water (12 g), and hydroxylamine hydrochloride (1.6 g). The mixture was heated under reflux for 10 hours. After cooling to room temperature, the precipitate was collected by filtration and dried sufficiently to obtain Intermediate 1B (2.8 g: yield 96%).

[Example 1-3] Compound No. Preparation of 1 (oxime ester compound of the present invention) Intermediate 1B (2.1 g) and dimethylformamide (15 g) were charged in a four-necked flask, and then triethylamine (1.7 g) and acetyl chloride (1) under ice cooling. .3 g) was charged. After stirring at room temperature for 2 hours, ion-exchanged water (15 g) and ethyl acetate (30 g) were charged and oil-water separation was performed. The organic layer was washed 3 times with water, desolvated, and then purified with a silica gel column (hexane / ethyl acetate = 50/50) to give compound No. 1 was obtained (1.4 g: yield 50%). The NMR data of 1 are shown in [Table 1].

[Examples 2-1 to 2-3] Compound No. 2 manufacturing

[Example 2-1] Production of intermediate 2A (ketone compound) After charging triphenylamine (5.9 g) and dichloroethane (40 g) in a four-necked flask, aluminum chloride (10.5 g) under ice cooling, Propionyl chloride (7.1 g) was added. After stirring at room temperature for 5 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with a 5% HCl aqueous solution, and further washed 4 times with water. The product layer was desolvated and then purified by a silica gel column (hexane / ethyl acetate = 80/20) to obtain Intermediate 2A (3.9 g: yield 39%).

[Example 2-2] Production of intermediate 2B (oxime compound) Intermediate 2A (3.9 g) and dimethylformamide (24 g) were weighed in a four-necked flask, and 35% hydrochloric acid (3. 9 g) and isobutyl nitrite (3.9 g) were added dropwise, and the mixture was stirred at room temperature for 20 hours. Ion-exchanged water (24 g) and ethyl acetate (48 g) were added, oil and water were separated, and the organic layer was washed 3 times. After desolvating the organic layer, an intermediate NCIx175-b was obtained (4.5 g: yield 96%).

[Example 2-3] Compound No. Preparation of 2 (oxime ester compound of the present invention) Intermediate 2B (4.5 g) and tetrahydrofuran (23 g) were charged into a four-necked eggplant flask, and triethylamine (3.0 g) and acetyl chloride (2.2 g) were added under ice cooling. ) Was sequentially added dropwise, and the mixture was stirred at room temperature for 2 hours. Ion-exchanged water (17 g) and ethyl acetate (46 g) were added, oil-water separation was performed, and the organic layer was washed 5 times. After desolvating the organic layer, purification was carried out using a silica gel column (hexane / ethyl acetate = 50: 50), and the compound No. 2 was obtained (2.7 g: yield 48%). Obtained compound No. The NMR data of 2 is shown in [Table 1].

[Examples 3-1 to 3-4] Compound No. Manufacture of 133

[Example 3-1] Production of intermediate 133A A four-necked flask was charged with fluorobenzene (27.7 g) and dichloroethane (192 g), and then cooled under ice with aluminum chloride (40.4 g) and n-octanoyl chloride. (46.8 g) were charged in order. After reacting at room temperature for 1 hour, the reaction solution was poured into ice-cooled 5% dilute hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with 5% diluted hydrochloric acid and three times with ion-exchanged water, and then desolvated to obtain intermediate 133A (50.0 g: yield 78%).

[Example 3-2] Production of intermediate 133B (nitrogen-containing compound) Carbazole (20.0 g), intermediate 133A (29.3 g), potassium carbonate (24.8 g), dimethyl sulfoxide (133 g) were placed in a four-necked flask. ) Was charged and reacted at 160 ° C. for 6 hours. Ion-exchanged water (173 g) was added, and extraction was performed with dichloroethane (163 g). The organic layer was washed 3 times with water and then desolvated to obtain Intermediate 133B (41.2 g: yield 93%).

[Example 3-3] Production of intermediate 133C (ketone compound) After charging intermediate 133B (41.2 g) and dichloroethane (209 g) in a four-necked flask, aluminum chloride (49.1 g) under ice cooling, n-Octanoyl chloride (39.9 g) was sequentially charged. After reacting for 4 hours at the same temperature, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with 5% dilute hydrochloric acid and three times with ion-exchanged water, and then desolvated to obtain Intermediate 133C (50.5 g: 73%).

[Example 3-4] Compound No. Production of 133 (oxime ester compound) Intermediate 133C (10.0 g), dimethylformamide (50 g), hydroxylamine hydrochloride (3.7 g) and pyridine (4.2 g) were added to a four-necked flask, and the mixture was heated at 80 ° C. for 10 minutes. Stir for hours. After cooling with ice-cooling, triethylamine (5.4 g) and acetyl chloride (4.2 g) were added in this order, and the mixture was stirred at room temperature for 5 hours. Ion-exchanged water (50 g) was added, and extraction was performed with ethyl acetate (100 g). The organic layer was washed with water three times, desolvated, and purified by a silica gel column (ethyl acetate / hexane = 1/4) to give compound No. 133 was obtained (2.3 g: 18% yield). Obtained compound No. The NMR data of 133 is shown in [Table 1].

[Examples 4-1 and 4-2] Compound No. Manufacturing 134

[Example 4-1] Production of intermediate 134A (oxime compound) Intermediate 133C (10.0 g) and DMF (10.0 g) were weighed in a four-necked flask, and 35% hydrochloric acid (6. 70 g) and isobutyl nitrite (6.63 g) were added dropwise, and the mixture was stirred at room temperature for 20 hours. Ion-exchanged water (22.8 g) and ethyl acetate (34.2 g) were added, oil and water were separated, and the organic layer was washed 3 times with water. The organic layer was desolvated and then purified with a silica gel column (ethyl acetate / hexane = 1/4) to obtain intermediate 134A (2.8 g: yield 25%).

[Example 4-2] Compound No. Production of 134 (oxime ester compound) Intermediate 134A (2.7 g) and ethyl acetate (10 g) were charged in a four-necked eggplant flask. Under ice cooling, triethylamine (1.3 g) and acetyl chloride (1.0 g) were sequentially added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. Ion-exchanged water (12 g) was added, oil-water separation was performed, and the organic layer was washed 5 times. The organic layer was desolvated and then purified with a silica gel column (hexane / ethyl acetate = 85: 15) to give compound No. 134 was obtained (0.89 g: yield 27%).
Obtained compound No. The NMR data of 134 is shown in [Table 1].

[Production Example 1] Blue pigment dispersion liquid No. Production of 1 DISPERBYK-161 (12.5 parts by mass; manufactured by Big Chemie Japan) as a dispersant, Pigment Blue 15: 6 (15 parts by mass) as a colorant, PGMEA (72.5 parts by mass), and a bead mill. Used to disperse to produce a blue pigment dispersion.

[Examples 5 to 7 and Comparative Examples 1 and 2] Preparation of Photosensitive Composition Each component was prepared according to the formulations shown in [Table 2] and [Table 3], and the photosensitive composition No. 1 to 3 and Comparative Photosensitive Composition No. 1-2 were obtained. The numbers in the table represent parts by mass. Compound No. as a photopolymerization initiator. 2, No. 133, No. 134, No. A2-3, and No. A2-11 was used alone.
The symbols in the table represent the following components.
A-1 Compound No. Two
A-2 Compound No. 133
A-3 Compound No. 134
A'-4 Compound No. A2-3
A'-5 Compound No. A2-11
B-1 SPC-3000 ^* (ethylenically unsaturated compound having an acid group,
42 wt% solids PGMEA solution; Showa Denko)
B-2 Kayarad DPHA
(Ethylenically unsaturated compound; manufactured by Nippon Kayaku)
C-1 Blue pigment dispersion liquid No. 1 (Coloring agent PGMEA dispersion liquid)
D-1 KBE-403 (Silane coupling agent; manufactured by Shin-Etsu Chemical)
D-2 F-554 (fluorine-containing group / lipophilic group-containing oligomer; manufactured by DIC)
E-1 PGMEA (solvent)
^* SPC-3000 is both an ethylenically unsaturated compound (B) and an alkali developable compound (D).

[Evaluation of cured product obtained from photosensitive composition]
The photosensitive composition No. 1 to 3 and Comparative Photosensitive Composition No. The brightness of the cured products obtained from Nos. 1 and 2 was evaluated by the following procedure. The results are also shown in [Table 4].

(Luminance)
On the glass substrate, the above-mentioned photosensitive composition No. 1 to 3 and Comparative Photosensitive Composition No. 1 and 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Thereafter, a high pressure mercury lamp was used to irradiate 100 mJ / cm ² to prepare an evaluation sample. The Y value was obtained from the transmittance of the obtained sample at 380 to 780 nm in accordance with JIS Z8701. The case where the Y value was 9.5 or more was designated as A, and the case where the Y value was less than 9.5 was designated as B. The higher BY value means higher brightness, which is useful. The one having a brightness evaluation of A can be preferably used for a color filter, and the one having a brightness evaluation of B is not suitable as a color filter.

[Evaluation of photosensitive composition]
In the above-mentioned evaluation of brightness, the photosensitive composition No. A having an evaluation of A. 1, 3 and Comparative Photosensitive Composition No. The sensitivity evaluation of 1 was performed by the following procedure. The results are also shown in [Table 5].

(sensitivity)
On the glass substrate, the above-mentioned photosensitive composition No. 1 to 3 and Comparative Photosensitive Composition No. 1 and 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask using a high pressure mercury lamp. After development using 2.5% by mass <sodium carbonate aqueous solution as a developing solution, it was thoroughly washed 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 / cm ² was observed with an electron microscope, and the line width of the mask opening of 30 μm was measured. A having a line width of 35 μm or more is A, B having a line width of 25 μm or more, and C having a line width of less than 25 μm. The larger the line width, the better the sensitivity. The photosensitive compositions having sensitivity evaluations of A and B can be used for color filters, and the photosensitive composition having sensitivity evaluation of A is particularly preferable. The photosensitive composition having a sensitivity evaluation of C is not suitable for use as a color filter.

  From the above [Table 3] to [Table 5], it is clear that the oxime ester compound of the present invention has high sensitivity and the cured product of the present invention has high brightness.

  Therefore, the oxime ester compound of the present invention is useful as a photopolymerization initiator because it has excellent photolithographic properties and the brightness of the obtained cured product is excellent.

  The oxime ester compound of the present invention is a novel compound having high sensitivity and excellent heat resistance (low sublimation property) and useful as a photopolymerization initiator, and particularly useful as a photopolymerization initiator. In particular, the oxime ester compound of the present invention is useful because a photosensitive composition containing the photopolymerization initiator can provide a color filter having high brightness and a display device containing the color filter.

Claims (9)

An oxime ester compound represented by the following general formula (I).

(In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R < ⁷ >, R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R <^11> , R <^12> , and R <^13> are each independently the following. Group represented by formula (II), hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, amino group, R ²¹ , OR ²¹ , SR ²¹ , NR ²² R ²³ , COR ²¹ , SOR ²¹ , SO ₂ R ²¹ or CONR ²² R ²³ ,
At ^{least three of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are of the following general formula (II ) Is a group represented by
R ²¹ , R ²² and R ²³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
The hydrogen atom in the groups represented by R ²¹ , R ²² and R ²³ is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group. , A mercapto group, an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms may be substituted,
Methylene groups in the group represented by R ^{21, R 22} and ^{R 23} is -O -, - CO -, - COO -, - OCO -, - NR 24 -, - NR 24 CO -, - S -, - _{CS -, - SO 2 -,} - SCO -, - COS -, - OCS- or CSO- in may be substituted,
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X ¹ represents absent, a direct bond, —CO—, —O— or —S—. )

(In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms. ,
The hydrogen atom in the group represented by R ³¹ and R ³² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, It may be substituted with an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
Methylene groups in the group represented by R ³¹ and ^{R 32} -O -, - CO -, - COO -, - OCO -, - NR 33 -, - NR 33 CO -, - S -, - CS-, _{-SO 2 -, - SCO -,} - COS -, - OCS- or CSO- in some cases be substituted,
R ³³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1, and * represents a bond. ) The oxime ester compound according to claim 1, wherein at least one of R ³ , R ⁶ and R ^{11 in} the general formula (I) is a group represented by the general formula (II).   A photopolymerization initiator containing the oxime ester compound according to claim 1.   A photosensitive composition containing the photopolymerization initiator (A) according to claim 3 and an ethylenically unsaturated compound (B).   The photosensitive composition according to claim 4, further comprising a colorant (C).   An alkali-developable photosensitive resin composition containing the photosensitive composition according to claim 4 or 5 and an alkali-developable compound (D).   A cured product of the photosensitive composition according to claim 4 or 5, or the alkali-developable photosensitive resin composition according to claim 6.   A display device containing the cured product according to claim 7.   A method for producing a cured product, comprising a step of curing the photosensitive composition according to claim 4 or 5 or the alkali developable photosensitive resin composition according to claim 6 by light irradiation or heating.