JP7248573B2 - Oxime ester compound and photopolymerization initiator containing said compound - Google Patents

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 photosensitive composition containing the photopolymerization initiator and an ethylenically unsaturated compound. relating to sexual compositions.

The photosensitive composition is obtained by adding a photopolymerization initiator to an ethylenically unsaturated compound, and can be polymerized and cured by irradiation with energy rays (light). , various photoresists, etc.

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 Literatures 1 and 2 cannot achieve both sensitivity, heat resistance (low sublimation property) and transparency (color filter with high brightness) at a satisfactory level.

Further, since the colored alkali-developable photosensitive composition containing a colorant such as a color filter is required to have high sensitivity, it is necessary to increase the concentration of the photopolymerization initiator in the resist. However, a photopolymerization initiator with a high concentration of photopolymerization initiator causes the generation of residue due to deterioration of developability, contamination of photomasks and heating furnaces with sublimation, and coloring of the cured product, resulting in poor brightness. was

WO2008/138732 WO2017/033880

Accordingly, an object of the present invention is to provide an oxime ester compound useful as a photopolymerization initiator with high sensitivity and high transmittance in the visible light region, a photopolymerization initiator using the compound, and a photosensitive composition, An object of the present invention is to provide a color filter with high luminance and a display device containing the color filter.

The present invention solves 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。）

(wherein 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 Group represented by general 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 , _SO2R21 ^{or CONR22R23 ,}
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 have 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 heterocyclic ring-containing group having 2 to 20 carbon atoms;
Hydrogen atoms in the groups represented by R ²¹ , R ²² and R ²³ are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups and vinyl ether groups. , may be substituted with a mercapto group, an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
The methylene groups in the groups represented by R ²¹ , R ²² and R ²³ are -O-, -CO-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -S-, - may be substituted with CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-;
R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X ¹ represents absence, 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。）

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

[2] The oxime ester compound according to [1], wherein at least one of R ³ , R ⁶ and R ¹¹ in general formula (I) is a group represented by 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 of [4], further comprising a coloring agent (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 described in [4] or [5] or the alkali-developable photosensitive resin composition described in [6].

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

[9] A method for producing a cured product, comprising the step of curing the photosensitive composition described in [4] or [5] or the alkali-developable photosensitive resin composition described in [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 general formula (I). The oxime ester compound has geometric isomers due to the double bond of oxime, but these are not distinguished.
That is, in the present specification, the compound represented by the general formula (I) and its exemplary compounds represent one or a mixture of two or more of these geometric isomers, and the structure showing a specific isomer is not limited to

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

Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl and isooctyl. , 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl, etc., with alkyl groups having 1 to 10 carbon atoms being particularly preferred.

Examples of alkenyl groups 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-tetradecatrienylallyl and the like. Alkenyl groups having 1 to 10 carbon atoms are particularly preferred.

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

The above-mentioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is replaced with a cycloalkyl group. For example, cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and deca and hydronaphthylpropyl.

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 and anthryl. be done.

The above arylalkyl group having 7 to 30 carbon atoms means a group having 7 to 30 carbon atoms in which the hydrogen atoms of the alkyl group are replaced with aryl groups. Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl.

Among the above hydrocarbon groups having 1 to 20 carbon atoms, since they are sensitive as photopolymerization initiators, alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 to 3 carbon atoms Cycloalkyl groups of 10, cycloalkylalkyl groups of 4 to 15 carbon atoms, aryl groups of 6 to 15 carbon atoms and arylalkyl groups of 7 to 15 carbon atoms are particularly preferred.

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

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

Among the above heterocyclic ring-containing groups having 2 to 20 carbon atoms, heterocyclic ring-containing groups having 2 to 10 carbon atoms are particularly preferable because they are highly sensitive as photopolymerization initiators.

As the hydrocarbon group having 1 to 20 carbon atoms represented by R ³¹ to R ³³ in the general formula (II), the number of carbon atoms represented by R ²¹ to R ²⁴ in the general formula (I) The same as 1 to 20 hydrocarbon groups can be mentioned.

Hydrogen atoms in the heterocyclic ring-containing groups having 2 to 20 carbon atoms represented by R ³¹ and R ³² and the groups represented by R ³¹ and R ³² in the general formula (II) may be substituted. Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R ²¹ to R ²³ in the general formula (I).

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

Halogen atoms in the general formulas (I) and (II) include fluorine, chlorine, bromine and iodine.

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

When R ¹ to R ¹³ are groups other than those of general formula (II), hydrogen atoms or cyano groups, particularly hydrogen atoms, are preferred as R ¹ to R ¹³ because they are easy to synthesize.

At least one, preferably two, and more preferably all of R ³ , R ⁶ and R ¹¹ in general formula (I) are groups represented by general formula (II). It is preferable because of good yield and easy purification. When all of R ³ , R ⁶ and R ¹¹ in general formula (I) are groups represented by general formula (II), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , Oxime ester compounds in which R ⁹ , R ¹⁰ , R ¹² and R ¹³ are hydrogen atoms are preferred because they are easy to synthesize.

A cured product obtained by using an oxime ester compound in which n=1 in the general formula (II) as the photopolymerization initiator (A) is preferable because of excellent transparency and brightness.

In the general formula (II) above, those in which R ³¹ is an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 7 carbon atoms are preferred because they are highly soluble in organic solvents. Those in which R ³² is an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, an ethyl group, or a phenyl group are preferred due to their high reactivity.

Preferred specific examples of the oxime ester compound of the present invention represented by the general formula (I) include the following compound Nos. 1 to No. 261. However, the present invention is not limited by 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 general formula (II) is 0, it can be synthesized according to 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 obtain an oxime compound. get 1. 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 oxime ester compound can also be produced by the method described in WO 2008/078678.

In the above reaction scheme, 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 , R in general formula (I) and general formula (II) ¹² , R ¹³ , R ³¹ , R ³² and X ¹ .

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

In the above reaction scheme, 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 , R in general formula (I) and general formula (II) ¹² , R ¹³ , R ³¹ , R ³² and X ¹ .

The novel oxime ester compound of the present invention described above is useful for pharmaceuticals, agricultural chemicals, base generators, photopolymerization initiators, and the like. polymerization initiator). Moreover, the novel oxime ester compound of the present invention can also be suitably used as a sensitizer.

The photosensitive composition of the present invention contains the photopolymerization initiator (A) and the ethylenically unsaturated compound (B) of the present invention, and optionally includes 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 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 30-100% by mass, more preferably 50-100% by mass.
Moreover, 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 general formula (I) are not particularly limited as long as they generate radicals upon irradiation with light, and conventionally known compounds can be used, for example, oxime ester compounds. , acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, phosphine oxide-based compounds, and titanocene-based compounds.

Examples of the oxime ester compound include compounds having a group represented by the general formula (II). Among the above photopolymerization initiators, the sensitivity is good, so the photosensitive composition of the present invention can be used. It can be preferably used.

The hydrocarbon groups having 1 to 20 carbon atoms represented by R ³¹ to R ³³ in the above general formula (II) are the hydrocarbon groups having 1 to 20 carbon atoms described in general formula (I). It is the same.

R ³¹ and R ³² in the above general formula (II) and the heterocyclic ring-containing group having 2 to 20 carbon atoms which may modify the group represented by R ³¹ or R ³² are represented by general formula (I) is the same as the heterocyclic ring-containing group having 2 to 20 carbon atoms described in .

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

(Wherein, R ³¹ , R ³² and n are respectively the same as R ³¹ , R ³² and n in general formula (II),
R ⁴¹ and R ⁴² each independently represents 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 a an arylalkyl group or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
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 no bond, direct bond, hydrocarbon group having 1 to 20 carbon atoms, CO, and R ⁴³ to R ⁴⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or represents a heterocyclic ring-containing group having 2 to 20 carbon atoms, wherein the hydrogen atom in the groups represented by R ⁴³ to R ⁴⁶ is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, or methacryloyl; group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, heterocyclic ring-containing group, and the methylene groups in the groups represented by R ⁴¹ to R ⁴⁶ are not adjacent to oxygen. may be substituted with -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, -SCO- or -COS- under certain conditions;
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 a number from 0 to 3; )

The hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ in the general formula (III) are the hydrocarbon groups having 1 to 20 carbon atoms described in the general formula (I), respectively. It is the same as the base.

The heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ in the general formula (III) is the heterocyclic ring-containing carbon atom described in 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 Nos. A2-1 to No. A2-28. However, the polymerization initiator (A) used in the present invention is not restricted by the following compounds.

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

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

Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2 -methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexylphenyl 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- and methyl-1-propan-1-one.

Benzyl etc. are mentioned as said benzyl type compound.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenylsulfide. be done.

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

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

Commercially available radical initiators include Adeka Optomer N-1414, N-1717, N-1919, Adeka Arcules NCI-831, NCI-930 (manufactured by ADEKA); 01, IRGACURE OXE 02, IRGACURE784 (manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (manufactured by TRONLY);

In the photosensitive composition of the present invention, the content of the photopolymerization initiator (A) is not particularly limited, but 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. Examples include ethylene, propylene, butylene, isobutylene, vinyl chloride, and vinylidene chloride. , vinylidene fluoride, unsaturated aliphatic hydrocarbons such as 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, mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone Polymer mono(meth)acrylate having a carboxyl group and 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, 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)acrylate ) 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 and polyhydric alcohols or polyhydric alcohols such as pentaerythritol tri(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester (meth)acrylate oligomers Esters of phenol; 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-anhydride Acid anhydrides of unsaturated polybasic acids such as leic acid adducts, dodecenyl succinic anhydride, and methylhimic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriamine tris(meth)acrylamide, xylylenebis(meth) Amides of unsaturated monobasic acids and polyvalent amines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth)acrylamide; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol , vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether and other unsaturated aromatic compounds; methyl vinyl ketone and other unsaturated ketones; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine, etc. 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; indenes 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 compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds.

Commercially available products can be used as the ethylenically unsaturated compound (B), for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by 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 and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Among them, polymer mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends, polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups, unsaturated mono Esters of basic acids and polyhydric alcohols or polyhydric phenols are suitable for the alkali-developable photosensitive resin composition of the present invention.

The ethylenically unsaturated compounds can be used alone or in combination of two or more. When two or more are used in combination, they are copolymerized in advance and used as a copolymer. may

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

Examples of the pigments include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; ∼200 mg/g of resin adsorbed, carbon black subjected to acid or alkaline surface treatment, 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. _Graphite , graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel ^, fullerene Aniline Black, Pigment Black 7, Titanium Black; Chromium Oxide Green, Miloli Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine, Prussian Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate , yellow lead, zinc yellow, red iron (III) oxide, cadmium red, synthetic iron black, amber, and other organic or inorganic pigments can be used. These pigments can be used alone or in combination.

Commercially available pigments can also be used as the above pigments. 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, Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110; 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, and phthalocyanine dyes. , dyes such as cyanine dyes, etc., and these may be used in combination.

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, based on 100 parts by mass of the ethylenically unsaturated compound (B). part by mass.

The photosensitive composition of the present invention may further contain an alkali-developable compound (D) to form an alkali-developable photosensitive resin composition. A composition containing both a coloring agent (C) and an 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 aqueous alkali solution, and examples thereof include resins described in JP-A-2004-264414.

Examples of the alkali-developable compound (D) include acrylic acid ester copolymers, phenol novolac epoxy resins, cresol novolac epoxy resins, polyphenylmethane-type epoxy resins having multifunctional epoxy groups, epoxy acrylate resins, carboxyl group A polymer having a resin obtained by reacting an epoxy group of an epoxy compound such as an epoxy compound represented by the following general formula (IV) with an unsaturated monobasic acid and further with a polybasic acid anhydride. be able to.
The epoxy acrylate resin is obtained by reacting (meth)acrylic acid on an epoxy compound, and examples thereof include Ripoxy SPC-2000, Dicklight UE-777 manufactured by DIC, and U-PICA 4015 manufactured by Japan U-PICA. can be mentioned.
Among these compounds, epoxy acrylate resins and polymers having carboxyl groups are preferred.

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)"). In addition to the structural unit (U1), the polymer having a carboxyl group has a structural unit (hereinafter referred to as " (hereinafter referred to as "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 (hereinafter referred to as "structural unit (U4)") other than the structural units (U1) to (U3).

The structural unit (U1) is a structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)"). is preferred.
Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids.
Examples of the above monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid and 2-methacryloyloxyethylhexa Hydrophthalic acid and the like can be mentioned.
Examples of the dicarboxylic acid include maleic acid, fumaric acid and citraconic acid.
Examples of the anhydride of the dicarboxylic acid include the anhydride of the dicarboxylic acid described above.
Among these compounds, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride is selected from the standpoint of copolymerization reactivity and solubility of the resulting copolymer in a developing solution. Acids are particularly preferred.
The polymer having a carboxyl group may have one type of structural unit (U1) derived from one type of compound (u1), or two or more types of structural units (U1) derived from two or more types of compounds (u1). It 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)acrylate oxiranyl (cyclo)alkyl ester, α-alkylacrylate oxiranyl (cyclo)alkyl ester, and a glycidyl ether compound having a polymerizable unsaturated bond. be done.
Examples of polymerizable unsaturated compounds having an oxetanyl group include (meth)acrylic acid esters having an oxetanyl group.

Specific examples of oxiranyl (cyclo)alkyl (meth)acrylate include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylate 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and 3,4- epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate and the like.
Specific examples of oxiranyl(cyclo)alkyl α-alkyl acrylate include glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6 ,7-epoxyheptyl and 3,4-epoxycyclohexyl α-ethylacrylate.
Specific examples of glycidyl ether compounds having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.
Specific examples of (meth)acrylic acid esters 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)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane and the like.
Among these compounds, in particular glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo[5.2.1 .0 ^2.6 ]decyl methacrylate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyl Oxymethyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane is preferred from the standpoint of polymerizability.
The polymer having a carboxyl group may have one type of structural unit (U2) derived from one type of compound (u2), or two or more types of structural units (U2) derived from two or more types of compounds (u2). It may have a structural unit (U2).

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

(Wherein, R ¹⁰⁰⁰ and R ¹⁰⁰¹ each independently represent a hydrogen atom or a methyl group,
u represents an integer from 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, * 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 formula (U) ¹⁰⁰² becomes the formula (Uα). When a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer having a carboxyl group, R ¹⁰⁰² in formula (U) becomes formula (Uβ).

The reaction between the unsaturated compound such as (meth)acrylic acid ester having a carboxyl group and an epoxy group in the polymer described above is carried out in the presence of a suitable catalyst as necessary, preferably in the presence of a polymerization inhibitor. It is preferable to add an unsaturated compound having an epoxy group to the solution of and stir for a predetermined time under 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 the total structural units of the polymer having a carboxyl group. %, 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 poor development during development can be reduced, and generation of 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)acryloyloxypropylmethyldimethoxysilane. ) acryloyloxypropyltriethoxysilane and the like.
When the polymer having a carboxyl group has a structural unit U3, it may have one structural unit (U3) derived from one compound (u3), and two or more compounds (u3) It may have two or more structural units (U3) derived from it.

The structural unit (U4) is a structural unit other than the above (U1) to (U3), and a polymerizable unsaturated compound other than the above (u1) to (u3) (hereinafter referred to as "compound (u4)"). It is preferably a structural unit derived from.
Examples of the compound (u4) include (meth)acrylic acid alkyl esters, (meth)acrylic acid cycloalkyl esters, (meth)acrylic acid aryl esters, (meth)acrylic acid aralkyl esters, unsaturated dicarboxylic acid dialkyl esters, (Meth)acrylic acid esters, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds having an oxygen-containing hetero-5-membered ring or an oxygen-containing hetero-6-membered ring can be mentioned.
Specific examples of (meth)acrylic acid alkyl esters include methyl acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. Examples include sec-butyl acid and t-butyl (meth)acrylate.
Specific examples of cycloalkyl (meth)acrylates include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.0 ^2,6 ] decan-8-yl, 2-(tricyclo[5.2.1.0 ^2,6 ]decan-8-yloxy)ethyl (meth)acrylate and isobornyl (meth)acrylate.
Specific examples of the (meth)acrylic acid aryl ester include, for example, phenyl acrylate.
Specific examples of (meth)acrylic acid aralkyl esters include, for example, benzyl (meth)acrylate.
Specific examples of unsaturated dicarboxylic acid dialkyl esters include diethyl maleate and diethyl fumarate.
Specific examples of (meth)acrylic acid esters having a five-membered oxygen-containing heterocyclic ring or a six-membered oxygen-containing heterocyclic ring include, for example, tetrahydrofuran-2-yl (meth)acrylate and tetrahydropyran-2-(meth)acrylate. and 2-methyltetrahydropyran-2-yl (meth)acrylate.
Specific examples of vinyl aromatic compounds include styrene and α-methylstyrene.
Specific examples of conjugated diene compounds include 1,3-butadiene and isoprene.
Specific examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.
Among the compounds (u4) listed above, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo[5.2.1.0 ^2,6 ] decan-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 structural unit (U4) derived from one compound (u4), two or more compounds (u4 ) may have two or more structural units (U4) derived from

A polymer having a preferable carboxyl group in the present embodiment is synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above compounds (u1) to (u4), respectively, in the following proportions. can be done.
Further, a (meth)acryloyloxy group is formed 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. can have a structural unit having

Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more 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%, still more preferably 25 mol% to 50 mol%

A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compounds (u1) to (u4) in the above range has good applicability. Since high resolution is achieved without loss, it is possible to obtain a cured film having a highly adjusted balance of physical properties even with a fine pattern, which is preferable.

The weight average molecular weight (Mw) of the carboxyl group-containing polymer is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. By using a polymer having a carboxyl group and having an Mw within this range, high resolution is achieved without impairing good coatability, so even with high-definition patterns, the balance of characteristics can be adjusted to a high degree. It is possible to give a cured film having a
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).

A 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.

Solvents used for polymerization of mixtures of polymerizable unsaturated compounds include, for example, 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, and propylene glycol monomethyl. Ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol and the like can be mentioned. These solvents may be used singly or in combination of two or more.

The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis-(2,4-dimethylvaleronitrile), '-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis(2-methylpropionate), 2, Azo compounds such as 2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) can be mentioned. These radical polymerization initiators may be used singly or in combination of two or more.

Among the polymers having a carboxyl group, the polymer described in JP-A-2005-234362, the epoxy group of the epoxy compound represented by the following general formula (VI), reacted with an unsaturated monobasic acid, further A polymer obtained by reacting a polybasic acid anhydride is preferred.

Examples of the alkali-developable compound (D) include acrylic acid ester copolymers, phenol and/or cresol novolac epoxy resins, polyphenylmethane-type epoxy resins having multifunctional epoxy groups, epoxy acrylate resins, and the following general A resin obtained by reacting an epoxy group of an epoxy compound such as an epoxy compound represented by formula (III) with an unsaturated monobasic acid and further with a polybasic acid anhydride can be used. The epoxy acrylate resin referred to here is obtained by reacting (meth)acrylic acid to the above epoxy compound, and examples thereof include Ripoxy SPC-2000, Dicklight UE-777 manufactured by DIC, and manufactured by Japan U-Pica. Upica 4015 and the like can be mentioned.
Among them, epoxy acrylate resins and resins obtained by reacting an epoxy group of an epoxy compound represented by the following general formula (IV) with an unsaturated monobasic acid and further with a polybasic acid anhydride. is preferred.
In addition, it is preferable that the alkali-developable compound which may have an ethylenically unsaturated bond contains 0.2 to 1.0 equivalents of an unsaturated group.

（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, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO— ₂ , -SS-, -SO-, -CO-, -OCO- or a group represented by the following [Chemical 36], [Chemical 37] or [Chemical 38], wherein the alkylidene group is substituted with a halogen atom and 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 alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom,
When there are a plurality of R ⁵¹ and R ⁵² , they may be the same or different,
c is an integer from 0 to 4,
d is an integer from 0 to 4,
m is an integer from 0 to 10,
The optical isomers present when m is not 0 can be any isomers. )

(Wherein, Z ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group optionally substituted with 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 with an alkoxy group having 1 to 10 carbon atoms, Y ¹ is 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 above alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, e represents an integer of 0 to 5, * represents a bond represents a hand.)

(In the formula, * represents a bond.)

(wherein Y ² and Z ² are each independently an optionally halogen-substituted alkyl group having 1 to 10 carbon atoms, an optionally halogen-substituted alkyl group having 6 to 20 carbon atoms, 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 arylalkenyl group having 6 to 20 carbon atoms which may be optionally substituted with a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterogeneous group having 2 to 20 carbon atoms which may be substituted with a halogen atom represents a cyclic group or a halogen atom, the methylene group in the group represented by Y ² may be substituted with an unsaturated bond, -O- or -S-, and Z ^{2 is} may form a ring, f represents an integer of 0 to 4, g represents an integer of 0 to 8, h represents an integer of 0 to 4, i represents an integer of 0 to 4, The total number of h and i is an integer of 2 to 4, * represents a bond)

The unsaturated monobasic acid acting on the epoxy compound includes acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate/malate, hydroxyethyl acrylate/malate, hydroxypropyl methacrylate/malate, and hydroxypropyl. Acrylate-malate, dicyclopentadiene-malate and the like.

Examples of the polybasic acid anhydride to be acted after the unsaturated monobasic acid is acted include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellit Acid anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanehydrotrimellitate, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhimic 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 one epoxy group of the epoxy compound, one hydroxyl group of the epoxy adduct It is preferable that the number of acid anhydride structures of the polybasic acid anhydride is 0.1 to 1.0 per number.
The epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be reacted according to a conventional method.

The alkali-developable photosensitive resin composition of the present invention, which is one embodiment 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 optional components, components such as an inorganic compound and a solvent are contained in combination. Among the alkali-developable photosensitive resin compositions of the present invention, those containing the coloring agent (C) are also particularly referred to as the colored alkali-developable photosensitive resin compositions of the present invention.
The alkali-developable compound (D) may be used singly 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 the ethylenically unsaturated compound (B), the composition containing the alkali-developable compound (D) is a photosensitive composition and an alkali-developable photosensitive resin composition It is also a thing.

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

Examples of the monofunctional epoxy compounds 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-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether , benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy- 4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, 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 with even better characteristics can be obtained. It is preferable because it can
As the bisphenol-type epoxy compound, an 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, novolak epoxy compounds such as phenol novolak type epoxy compounds, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolak type epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane compounds; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer; glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol, and N,N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds; Triphenylmethane type epoxy compounds; A type epoxy compound or 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 alkali developability which may have an ethylenically unsaturated bond is the same as the alkali developability of the present invention. 1 to 20% by mass, preferably 3 to 12% by mass in the photosensitive resin composition.

A solvent can be further added to the photosensitive composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing the above components (photopolymerization initiator (A), ethylenically unsaturated compound (B), etc.) as needed, such as 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. Ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; ethylene glycol monomethyl ether, ethylene glycol mono cellosolve solvents such as ethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 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 and xylene; hexane, heptane, Aliphatic hydrocarbon solvents such as octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Mineral spirit, Swasol #310 (Cosmo Matsuyama Oil Co.), Solvesso #100 (Exxon Chemical Co.), etc. paraffin solvents; carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline ; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide (DMAc); Alternatively, it can be used as a mixed solvent of two or more.
Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. have good compatibility between the resist and the photopolymerization initiator (A) in the photosensitive composition. Therefore, it is preferable.

In addition, the photosensitive composition of the present invention may optionally contain p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents and sensitizers. , surfactant, silane coupling agent, melamine compound, thermal polymerization inhibitor; plasticizer; adhesion promoter; filler; antifoaming agent; leveling agent; anti-agglomeration agents; catalysts; effect accelerators; cross-linking agents;

A dispersant for dispersing the coloring agent (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 commercially available dispersants such as the BYK series manufactured by BYK-Chemie Japan can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and/or a quaternary salt thereof. and those having an amine value of 1 to 100 mgKOH/g are preferably used.

The latent additive is 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 six-membered alicyclic, aromatic 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, 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 —O—R 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, or an arylalkyl group having 7 to 20 carbon atoms. 20 heterocycle-containing groups or trialkylsilyl groups. )

（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。）

(Wherein, ring A ¹ and R ⁹¹ are the same as in general formula (A) above,
X ⁷ is a group represented by the following general formula (1), 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, 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 and 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 above general formula (1), X ⁸ is —CR ⁹⁷ R ⁹⁸ —, —NR ⁹⁹ —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic group having 6 to 35 carbon atoms, a hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, or any substituent represented by the following [Chemical 42] to [Chemical 44],
The methylene group in the aliphatic hydrocarbon group is -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a bond combining these without adjacent oxygen atoms may be substituted with
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 independently represents a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, _-SO2- , -SS-, -SO- or >NR ¹⁰⁰ ; ⁹⁹ and R ¹⁰⁰ are a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 35 carbon atoms. 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, R ¹⁰² represents an alkyl group having 1 to 10 carbon atoms, represents an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom; the above alkyl group, alkoxy group and alkenyl group may have a substituent; f is 0 to 5; is an integer, * 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 optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted C 6 to 20 aryl group, optionally substituted aryloxy group having 6 to 20 carbon atoms, optionally substituted arylthio group having 6 to 20 carbon atoms, having a substituent an arylalkenyl group having 6 to 20 carbon atoms which may be substituted, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, a heterogeneous group having 2 to 20 carbon atoms which may have a substituent represents ^a cyclic group or a halogen atom, the methylene group in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and ^R , b represents 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。）

(Wherein, k = 2 to 6, 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 is a group represented by the following general formula (4) when k = 4, represented by the following general formula (5) when k = 5, and represented by the following general formula (6) when k = 6 , R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, 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 ring A ¹ and R ⁸⁶ are the same as in general formula (A) above.)

（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, a represents an aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, and Z ¹¹ , Z ¹² and Z ¹³ are each independently a direct bond, -O-, -S-, >CO, -CO- O—, —O—CO—, —SO ₂ —, —SS—, —SO—, —NR ¹²¹ —, —PR ¹²¹ — or optionally substituted aliphatic having 1 to 35 carbon atoms represents a hydrocarbon group, an optionally substituted aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent,
R ¹²¹ is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 35 carbon atoms. or an optionally substituted heterocyclic group having 2 to 35 carbon atoms, wherein the methylene group in the aliphatic hydrocarbon group is a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O- or -SO ₂ - may be substituted. )

（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, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a number of carbon atoms represents a heterocyclic group of 2 to 35, wherein the methylene group in the aliphatic hydrocarbon group is substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- and Z ¹¹ to Z ¹⁴ are each independently a group in the same range as the groups 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 above 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 heterovalent hydrocarbon group 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 independently in the same range as the groups 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 above general formula (5), Y ¹⁴ is a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterovalent hydrocarbon group 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 independently in the same range as the groups 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, (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 Polyesters, phenol resins, phenoxy resins, polyamideimide resins, polyamic acid resins, epoxy resins and the like can be mentioned, and among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymers and epoxy resins are preferred.
When an organic polymer is used, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

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 oxidation of 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, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio 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 Nos. Aliphatic polyfunctional thiol compounds such as C1 and trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, Showa Denko Karenz MT BD1, PE1, NR1 and the like.

Examples of the above-mentioned surfactants include perfluoroalkyl phosphates, fluorine-based surfactants such as perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates, and alkyl sulfates; 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 and fatty acid monoglycerides; Amphoteric surfactants; Silicone surfactants Surfactants such as active agents can be used, and they 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. A silane coupling agent having a methacryloyl group or an epoxy group is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly)methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, and (poly)methylolurea. A compound in which (at least two) are alkyl-etherified, and the like can be mentioned.
Here, the alkyl group constituting the alkyl ether includes a methyl group, an ethyl group and a butyl group, which may be the same or different. In addition, methylol groups that are not alkyl-etherified may be self-condensed within one molecule, or may be condensed between two molecules to form 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 preferred.

As the leveling agent, existing leveling agents can be used as long as they have a leveling effect. Among them, silicone-based leveling agents and fluorine-based leveling agents are particularly preferably used.

As the silicone-based leveling agent, a commercially available silicone-based leveling agent can be used. 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 (manufactured by BYK-Chemie Japan); ACFS180, ACFS360, AC S20 (manufactured by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (manufactured by Kyoeisha Chemical); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (manufactured by Shin-Etsu Chemical Co., Ltd.); LP-7001, LP-7002, 8032ADDITIVE, 57ADDITIVE, L-7604, FZ-2110, FZ- Commercially available products such as 2105, 67ADDITIVE, 8618ADDITIVE, 3ADDITIVE, and 56ADDITIVE (manufactured by Dow Corning Toray Co., Ltd.) can be used.

As the fluorine-based leveling agent, commercially available fluorine-based leveling agents can be used. Surflon S-611, Surflon S-651, Surflon S-386 (manufactured by AGC Seimi Chemical); BYK-340 (manufactured by BYK-Chemie Japan); AC110a, AC100a (manufactured by AlginChemie); Megafac F-114, Megafuck F-410, Megafuck F-444, Megafuck EXPTP-2066, Megafuck F-430, Megafuck F-472SF, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck R-94, Megafuck RS-72-K, Megafuck RS-75, Megafuck F-556, Megafuck EXPTF-1367, Megafuck EXPTF-1437, Megafuck F-558, Megafac EXPTF-1537 (manufactured by DIC); FC-4430, FC-4432 (manufactured by Sumitomo 3M); Futergent 100, Futergent 100C, Futergent 110, Futergent 150, Futergent 150CH , Futergent AK, Futergent 501, Futergent 250, Futergent 251, Futergent 222F, Futergent 208G, Futergent 300, Futergent 310, Futergent 400SW (manufactured by Neos); PF-136A, PF -Use commercially available products such as 156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, PF-3320 (manufactured by Kitamura Chemical Industry) can be done.

In the photosensitive composition of the present invention, optional components other than 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 The amount of the components to be used is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total per 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 coating or varnish; a photocurable adhesive; a printed circuit board; color filters in liquid crystal display elements for color display of digital cameras, etc.; color filters for CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; Photoresists for engineering; electroplating resists; etching resists; dry films; solder resists; resists for forming structures of various display devices; optical switches; plating masks; etching masks; color test systems; glass fiber cable coatings; stencils for screen printing; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; Photoresist material of; can be used for various purposes such as a photoresist material used for forming a dielectric layer in the successive lamination of a printed circuit board or a protective film, and the use is not particularly limited.

The photosensitive composition or 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 the purpose of forming projections for vertically aligned liquid crystal display elements. In particular, it is useful as a photosensitive composition for simultaneously forming projections and spacers for vertically aligned liquid crystal display devices.

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

The photosensitive composition or alkali-developable photosensitive resin composition of the present invention can be coated with soda glass or quartz glass by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various types of printing, and immersion. , semiconductor substrates, metals, paper, plastics and the like. In addition, once applied onto a supporting substrate such as a film, it can be transferred onto another supporting substrate, and there are no restrictions on the method of application.

Further, as the light source of the energy beam used for curing the photosensitive composition alkali-developable photosensitive resin composition of the present invention, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, mercury Electromagnetic wave energy or electron beams with a wavelength of 2000 angstroms to 7000 angstroms obtained from vapor 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. , X-rays, and radiation can be used. Preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc., which emit light with a wavelength of 300 to 450 nm can be used. be done.

Furthermore, by using laser light as the exposure light source, the laser direct writing method, which forms images directly from digital information such as computers without using a mask, not only improves productivity but also improves resolution and positional accuracy. As the laser light, light with a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser , various semiconductor lasers, and YAG lasers, which emit light in the visible to infrared region, are also used. When using these lasers, a sensitizing dye is added that absorbs in the visible to infrared region of interest.

The spacer for a liquid crystal display panel described above comprises the steps of: (1) forming a coating film of the photosensitive composition of the present invention on a substrate; (3) baking after exposure; (4) developing the film after exposure; and (5) heating the film after development.

The photosensitive composition of the present invention to which an ink-repellent agent is added is useful as a partition wall-forming resin composition for an inkjet method, and the composition is used for a color filter, particularly for an inkjet method 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.

Partition walls formed from the photosensitive composition of the present invention partition the surface of the transfer medium, and an optical element is formed by a method in which liquid droplets are applied to the partitioned recesses on the transfer medium by an inkjet method to form an image area. manufactured. At this time, it is preferable that the droplets contain a coloring agent and the image area is colored, and at least a pixel group consisting of a plurality of colored areas and a partition separating each colored area of the pixel group are formed on the substrate. and an optical element manufactured by the method for manufacturing an optical element described above is preferably used.

EXAMPLES The present invention will be described in more detail below 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. 1 manufacturing

[Example 1-1] Preparation of Intermediate 1A (ketone compound) A four-necked flask was charged with triphenylamine (3.3 g) and dichloroethane (15 g), and then aluminum chloride (5.8 g) was added 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% dilute hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with a 5% HCl aqueous solution and then washed with water four times. After removing the solvent from the product layer, purification was performed using 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). , and heated to reflux for 10 hours. After cooling to room temperature, the precipitate was collected by filtration and thoroughly dried to obtain Intermediate 1B (2.8 g: yield 96%).

[Example 1-3] Compound No. Preparation of 1 (oxime ester compound of the present invention) A four-necked flask was charged with intermediate 1B (2.1 g) and dimethylformamide (15 g), and then triethylamine (1.7 g) and acetyl chloride (1 .3 g) was charged. After stirring at room temperature for 2 hours, ion-exchanged water (15 g) and ethyl acetate (30 g) were added to separate oil and water. The organic layer was washed with water three times, the solvent was removed, and purification was performed using a silica gel column (hexane/ethyl acetate=50/50). 1 (1.4 g: 50% yield). 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) A four-necked flask was charged with triphenylamine (5.9 g) and dichloroethane (40 g), and then aluminum chloride (10.5 g) was added 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% dilute hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with a 5% HCl aqueous solution and then washed with water four times. After removing the solvent from the product layer, purification was performed using 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 into a four-necked flask, and 35% hydrochloric acid (3.9 g) was added under ice cooling. 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 to separate oil and water, and the organic layer was washed with water three times. After desolvating the organic layer, 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 placed in a four-necked round-bottomed flask, and under ice-cooling, triethylamine (3.0 g) and acetyl chloride (2.2 g) were mixed. ) was added dropwise in order, and the mixture was stirred at room temperature for 2 hours. After adding ion-exchanged water (17 g) and ethyl acetate (46 g), oil-water separation was performed, and the organic layer was washed with water five times. After removing the solvent from the organic layer, purification was performed using a silica gel column (hexane/ethyl acetate=50:50). 2 was obtained (2.7 g: 48% yield). The resulting compound no. NMR data of 2 are shown in [Table 1].

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

[Example 3-1] Production of Intermediate 133A A four-necked flask was charged with fluorobenzene (27.7 g) and dichloroethane (192 g), and then aluminum chloride (40.4 g) and n-octanoyl chloride were added under ice cooling. (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 deionized water, and then the solvent was removed to obtain Intermediate 133A (50.0 g: yield 78%).

[Example 3-2] Preparation 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. ) 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 with water three times and then the solvent was removed 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) into a four-necked flask, aluminum chloride (49.1 g), n-Octanoyl chloride (39.9 g) was charged in order. After reacting at the same temperature for 4 hours, 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 deionized water, and then the solvent was removed to obtain intermediate 133C (50.5 g: 73%).

[Example 3-4] Compound No. Preparation 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 heated at 80°C for 10 minutes. Stirred for an hour. After cooling with ice, triethylamine (5.4 g) and acetyl chloride (4.2 g) were added dropwise in that 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). After the organic layer was washed with water three times, the solvent was removed and purified with a silica gel column (ethyl acetate/hexane=1/4). 133 was obtained (2.3 g: 18% yield). The resulting compound no. NMR data of 133 are shown in [Table 1].

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

[Example 4-1] Preparation of Intermediate 134A (oxime compound) Intermediate 133C (10.0 g) and DMF (10.0 g) were weighed into a four-necked flask, and 35% hydrochloric acid (6.0 g) was added under ice cooling. 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 to separate oil and water, and the organic layer was washed with water three times. After removing the solvent from the organic layer, purification was performed using a silica gel column (ethyl acetate/hexane=1/4) to obtain Intermediate 134A (2.8 g: yield 25%).

[Example 4-2] Compound No. Preparation of 134 (oxime ester compound) Intermediate 134A (2.7 g) and ethyl acetate (10 g) were placed in a four-neck eggplant flask. Under ice-cooling, triethylamine (1.3 g) and acetyl chloride (1.0 g) were added dropwise in order, and the mixture was warmed to room temperature and stirred for 3 hours. After adding ion-exchanged water (12 g), oil-water separation was performed, and the organic layer was washed with water five times. After removing the solvent from the organic layer, purification was performed using a silica gel column (hexane/ethyl acetate=85:15). 134 was obtained (0.89 g: 27% yield).
The resulting compound no. NMR data of 134 are shown in [Table 1].

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

[Examples 5 to 7 and Comparative Examples 1 to 2] Preparation of photosensitive composition Each component was prepared according to the formulations in [Table 2] and [Table 3]. 1 to 3 and Comparative Photosensitive Composition Nos. 1-2 were obtained. The numbers in the table represent parts by mass. As a photopolymerization initiator compound No. 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. 2
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,
Solid content 42 wt% PGMEA solution; manufactured by Showa Denko)
B-2 Kayalad DPHA
(Ethylenically unsaturated compound; manufactured by Nippon Kayaku)
C-1 Blue Pigment Dispersion Liquid No. 1 (colorant PGMEA dispersion)
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 alkaline developable compound (D).

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

(Luminance)
Photosensitive composition No. 1 was coated on a glass substrate. 1 to 3 and Comparative Photosensitive Composition Nos. 1 and 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds), pre-baked at 90° C. for 90 seconds using a hot plate, and then cooled at 23° C. for 40 seconds. After that, a high-pressure mercury lamp was used to irradiate 100 mJ/cm ² to prepare an evaluation sample. The Y value was determined according to JIS Z8701 from the transmittance of the obtained sample at 380 to 780 nm. A sample with a Y value of 9.5 or more was rated as A, and a sample with a Y value of less than 9.5 was rated as B. A higher BY value means higher luminance, which is useful. Those with a luminance evaluation of A can be preferably used as color filters, while those with a luminance evaluation of B are not suitable as color filters.

[Evaluation of photosensitive composition]
Photosensitive composition no. 1, 3 and Comparative Photosensitive Composition Nos. 1 sensitivity evaluation was performed by the following procedure. The results are also shown in [Table 5].

(sensitivity)
Photosensitive composition No. 1 was coated on a glass substrate. 1 to 3 and Comparative Photosensitive Composition Nos. 1 and 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds), pre-baked at 90° C. for 90 seconds using a hot plate, and then cooled at 23° C. for 40 seconds. After that, it was exposed through a mask using a high-pressure mercury lamp. After development using an aqueous solution of 2.5% by mass of sodium carbonate as a developer, the film was thoroughly washed with water and post-baked in an oven at 230° C. for 30 minutes 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 with a mask opening of 30 μm was measured. A was assigned to those with a line width of 35 µm or more, B was assigned to those with a line width of 25 µm or more, and C was assigned to those with a line width of less than 25 µm. The greater the line width, the better the sensitivity. The photosensitive compositions with a sensitivity evaluation of A and B can be used for color filters, and the photosensitive composition with a sensitivity evaluation of A is particularly preferred. A photosensitive composition with a sensitivity evaluation of C is not suitable for use as a color filter.

From the above [Tables 3] to [Tables 5], it is clear that the oxime ester compounds of the present invention have high sensitivity and the cured products of the present invention have high brightness.

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

The oxime ester compound of the present invention is a novel compound useful as a photopolymerization initiator with high sensitivity and excellent heat resistance (low sublimation), and is 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 with high luminance and a display device containing the color filter.

Claims (8)

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

(Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² and R ¹³ represent a hydrogen atom ,
R ³ , R ⁶ and R ¹¹ are groups represented by the following general formula (II),
X ¹ represents absence or a direct bond . )

(wherein 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 group having 2 to 20 carbon atoms,
A hydrogen atom in the groups 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, or may be substituted with isocyanate groups ,
The methylene groups in the groups represented by R ³¹ and R ³² are -O-, -CO-, -COO-, -OCO-, -NR ³³ -, -NR ³³ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO- in some cases,
R ³³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 1 and * represents a bond. ) A photopolymerization initiator containing the oxime ester compound according to claim 1 . A photosensitive composition comprising the photopolymerization initiator (A) according to claim 2 and an ethylenically unsaturated compound (B). 4. The photosensitive composition according to claim 3 , further comprising a coloring agent (C). An alkali-developable photosensitive resin composition comprising the photosensitive composition according to claim 3 or 4 and an alkali-developable compound. A cured product of the photosensitive composition according to claim 3 or 4 or the alkali-developable resin composition according to claim 5 . A display device containing the cured product according to claim 6 . A curing method comprising curing the photosensitive composition according to claim 3 or 4 or the alkali-developable photosensitive resin composition according to claim 5 by light irradiation or heating.