KR102818078B1 - Oxime ester compound and photopolymerization initiator containing said compound - Google Patents

Abstract

An oxime ester compound represented by the following general formula (I). (In the formula, at least three of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are groups represented by the following general formula (II). It is preferable that at least one of R ³ , R ⁶ and R ¹¹ is a group represented by the general formula (II).)

Description

Oxime ester compound and photopolymerization initiator containing said compound

The present invention relates to 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.

The photosensitive composition is an ethylenically unsaturated compound with a photopolymerization initiator added thereto, and can be polymerized and cured by irradiating it with energy rays (light), so it is used in photocurable inks, photosensitive printing plates, various photoresists, etc.

As a photopolymerization initiator used in the above photosensitive composition, Patent Document 1 discloses an oxime ester photopolymerization initiator having a carbazole skeleton. In addition, Patent Document 2 discloses a polymerization initiator having an oxime ester compound having a triarylamine skeleton. However, the oxime ester compounds described in Patent Documents 1 and 2 were not able to satisfy sensitivity, heat resistance (low sublimation), and transparency (high brightness of color filters) at a satisfactory level.

In addition, since a colored alkaline developing photosensitive composition containing a coloring agent such as a color filter is required to have high sensitivity, it is necessary to have a high concentration of the photopolymerization initiator in the resist. However, a photopolymerization initiator with a high concentration causes the generation of residue due to deterioration of developability, contamination of the photomask or furnace due to sublimation, and coloring of the cured product and low brightness.

International Publication WO2008/138732 International Publication WO2017/033880

Accordingly, the object of the present invention is to provide an oxime ester compound useful as a photopolymerization initiator having high sensitivity and high transmittance in the visible light region, a photopolymerization initiator using the compound, and a photosensitive composition, and to provide a color filter having high brightness 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).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an amino group, R ²¹ , OR ²¹ , SR ²¹ , NR ²² R ²³ , COR ²¹ , SOR ²¹ , SO ₂ R ²¹ or CONR ²² R ²³ ,

At least three of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are groups represented by the following general formula (II),

R ²¹ , R ²² and R ²³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

The hydrogen atoms in the groups represented by R ²¹ , R ²² and R ²³ may be substituted with 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, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms.

The methylene groups represented by R ²¹ , R ²² and R ²³ may be substituted with -O-, -CO-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or -CSO-.

R ²⁴ represents a hydrogen atom and a hydrocarbon group with 1 to 20 carbon atoms.

X ¹ represents the absence, direct bond, -CO-, -O-, or -S-.)

(In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

The hydrogen atoms in the groups represented by R ³¹ and R ³² may be substituted with 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, an isocyanate group, or a heterocyclic group having 2 to 20 carbon atoms.

The methylene group in the groups represented by R ³¹ and R ³² may be substituted with -O-, -CO-, -COO-, -OCO-, -NR ³³ -, -NR ³³ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or -CSO-.

R ³³ represents a hydrogen atom and a hydrocarbon group with 1 to 20 carbon atoms.

n represents 0 or 1, and * represents a combination number.)

[2] In [1],

An oxime ester compound in which 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 an oxime ester compound described in [1] or [2].

[4] A photosensitive composition containing a photopolymerization initiator (A) and an ethylenically unsaturated compound (B) described in [3].

[5] In [4],

A photosensitive composition additionally containing a colorant (C).

[6] An alkaline-developable photosensitive resin composition containing the photosensitive composition described in [4] or [5] and an alkaline-developable compound (D).

[7] A cured product of the photosensitive composition described in [4] or [5] or the alkaline developable photosensitive resin composition described in [6].

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

[9] A method for producing a cured product having a process of curing the photosensitive composition described in [4] or [5] or the alkaline 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 includes geometric isomers due to the double bond of oxime, but these are not distinguished.

That is, the compound represented by the general formula (I) in this specification and the exemplary compounds thereof represent one or a mixture of two or more of these geometric isomers, and are not limited to a structure representing a specific isomer.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ in the general formula (I) above is not particularly limited, and preferably represents an alkyl group 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 arylalkyl group having 7 to 20 carbon atoms.

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

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-tetradecatrienyllallyl. In particular, an alkenyl group having 1 to 10 carbon atoms is preferable.

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

The above cycloalkylalkyl group having 4 to 20 carbon atoms refers to a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is replaced by a cycloalkyl group. Examples thereof include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-adamantylpropyl, and decahydronaphthylpropyl.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, etc.

The above arylalkyl group having 7 to 30 carbon atoms refers to a group having 7 to 30 carbon atoms in which a hydrogen atom of an alkyl group is replaced by an aryl group. Examples thereof include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl.

Among the hydrocarbon groups having 1 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an arylalkyl group having 7 to 15 carbon atoms are particularly preferable in terms of good sensitivity as a photopolymerization initiator.

In the general formula (I) above, examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ²¹ to R ²³ and the heterocyclic group having 2 to 20 carbon atoms which may substitute a hydrogen atom in the group represented by R ^{21 to} R 23 include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, Examples thereof include urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidon-1-yl, 2,4-deoxyimidazolidin-3-yl, and 2,4-deoxyoxazolidin-3-yl.

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

Among the heterocyclic groups having 2 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms is particularly preferable in that it has good sensitivity as a photopolymerization initiator.

As the hydrocarbon group having 1 to 20 carbon atoms represented by R ³¹ to R ³³ in the general formula (II) above, examples thereof include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ in the general formula (I).

Among the heterocyclic group having 2 to 20 carbon atoms represented by R ³¹ and R ³² in the general formula (II) above, and the heterocyclic group having 2 to 20 carbon atoms which may substitute a hydrogen atom in the group represented by R ³¹ and R ³² , examples thereof include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R ²¹ to R ²³ in the general formula (I).

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

Halogen atoms in the above 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 it has excellent brightness when used as a photopolymerization initiator, and an oxime ester compound in which X ¹ is a direct bond is particularly preferable because it has even better sensitivity in addition to brightness. In the present invention, the absence of X ¹ means that no atom is present at the position of X ¹ and the oxime ester compound represented by the general formula (I) has a triphenolamine skeleton.

When R ¹ to R ¹³ are groups other than those in general formula (II), a hydrogen atom or a cyano group, particularly a hydrogen atom, is preferred as R ¹ to R ¹³ because it is easy to synthesize.

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

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

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

Preferred specific examples of the oxime ester compound of the present invention represented by the general formula (I) above include the following compounds No. 1 to No. 261. However, the present invention is not limited in any way by the following compounds.

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

When n in the general formula (II) is 0, it can be synthesized by the following reaction scheme. Specifically, a known nitrogen-containing compound is reacted with a known and commercially available acid chloride to obtain a ketone compound 1, and the obtained ketone compound 1 is reacted with hydroxylamine hydrochloride to obtain an oxime compound 1. Then, the oxime ester compound 1 of the present invention represented by the general formula (I) is obtained by reacting the oxime compound 1 with an acid chloride in the presence of triethylamine (TEA).

Oxime compounds and oxime ester compounds can also be prepared by the method described in International Publication No. WO2008/078678.

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

When n in general formula (II) is 1, it can be manufactured by the following method according to the following reaction formula.

That is, by reacting a known nitrogen-containing compound with an acid chloride, a ketone compound 2 is obtained, and by reacting the ketone compound 2 with isobutyl nitrite, an oxime compound 2 is obtained. Then, by reacting the oxime compound 2 with an acid anhydride or an acid chloride, an oxime ester compound 2 of the present invention represented by the general formula (I) is obtained.

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

The novel oxime ester compound of the present invention described above is useful as a pharmaceutical, pesticide, base generator, photopolymerization initiator, etc., and among photopolymerization initiators, it is particularly useful as a radical polymerization initiator (photoradical polymerization initiator or thermal radical polymerization initiator). In addition, 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 contains a combination of components such as a colorant (C), an alkaline developable compound (D), an inorganic compound, and a solvent.

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

In addition, the photopolymerization initiator (A) of the present invention is useful as a photopolymerization initiator of an ethylenically unsaturated compound (B).

Other photopolymerization initiators not included in the general formula (I) are not particularly limited and any known compound can be used as long as it generates radicals upon light irradiation. Preferred examples include oxime ester compounds, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds, and titanocene compounds.

As the above oxime ester compound, a compound having a group represented by the above general formula (II) can be exemplified, and since it has good sensitivity among the above photopolymerization initiators, it can be preferably used in the photosensitive composition of the present invention.

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

In the general formula (II), the group containing a heterocycle having 2 to 20 carbon atoms that modifies the group represented by R ³¹ and R ³² and R ³¹ or R ³² is the same as the group containing a heterocycle having 2 to 20 carbon atoms described in the general formula (I).

Among the oxime ester compounds having a group represented by the above general formula (II), a compound represented by the following general formula (III) is particularly highly sensitive and is therefore preferable for use in the photosensitive composition of the present invention.

Among the oxime ester compounds having a group represented by the above general formula (I), a compound represented by the following general formula (III) is particularly preferred for use in the photosensitive composition of the present invention because it has high sensitivity.

(In the formula, R ³¹ , R ³² and n are the same as R ³¹ , R ³² and n in the general formula (II), respectively,

R ⁴¹ and R ⁴² each independently represent a direct bond, a hydrogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle,

X ¹¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁴³ R ⁴⁴ , CO, NR ⁴⁵ or PR ⁴⁶ ,

X ¹² represents a non-bonded, direct bonded, 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 a group having 2 to 20 carbon atoms containing a heterocycle, and the hydrogen atom in the group represented by R ⁴³ to R ⁴⁶ may be substituted with 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 mercapto group, an isocyanate group, or a heterocycle-containing group, and the methylene group in the group represented by R ⁴¹ to R ⁴⁶ may be substituted with -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, -SCO-, or -COS- under the condition that the oxygens are not adjacent to each other.

R41~R46 may independently form a ring by joining with any 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) above are each identical to the hydrocarbon groups having 1 to 20 carbon atoms described in the general formula (I).

The group having 2 to 20 carbon atoms and containing a heterocycle represented by R ⁴¹ to R ⁴⁶ in the general formula (III) above is the same as the group having 2 to 20 carbon atoms and containing a heterocycle described in the general formula (I).

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

In the case where X ¹ in general formula (III) is a sulfur atom and X ² is not bonded, it is an oxime ester compound having a diphenyl sulfide skeleton represented by the above compounds No. A2-1 to A2-7, and it is preferable in that a photosensitive composition having good sensitivity is obtained by using it in combination with the oxime ester compound of the present invention as a polymerization initiator.

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

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-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidebenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, Examples thereof include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

The above benzyl compounds include benzyl, etc.

Examples of the above benzophenone compounds include benzophenone, o-benzoyl methyl benzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

The above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.

Examples of phosphine oxide compounds include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Titanocene compounds include bis(cyclopentadienyl)-bis[2,6-difluoro-3-(p-1-yl)]titanium.

Commercially available radical initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ACKLES NCI-831, NCI-930 (all from ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (all from BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all from TRONLY); etc.

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

The above 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, for example, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; Mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as (meth)acrylic acid, α-chloracrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], and ω-carboxypolycaprolactone mono(meth)acrylate; Unsaturated polybasic acids such as hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups; (Meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate glycidyl, the following compounds No. A1 to No. A4, (meth)acrylate 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 dimethylaminoethyl, (meth)acrylate aminopropyl, (meth)acrylate dimethylaminopropyl, (Meth)acrylic acid ethoxyethyl, (meth)acrylic acid poly(ethoxy)ethyl, (meth)acrylic acid butoxyethoxyethyl, (meth)acrylic acid ethylhexyl, (meth)acrylic acid phenoxyethyl, (meth)acrylic acid tetrahydrofuryl, (meth)acrylic acid vinyl, (meth)acrylic acid allyl, (meth)acrylic acid benzyl, 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, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate; Acid anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, and methylhimic anhydride; Amides of unsaturated monobasic acids and polyhydric amines such as (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl(meth)acrylamide; Unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; 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; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; Examples thereof include vinyl chloride, vinylidene chloride, divinylsuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinylurethane compounds of hydroxyl-containing vinyl monomers and polyisocyanate compounds, and vinylepoxy compounds of hydroxyl-containing vinyl monomers and polyepoxy compounds.

As the above ethylenically unsaturated compound (B), commercially available products can be used, and examples thereof include Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (products of Nippon Kayakusha), SPC-1000, SPC-3000 (products of Showa Denko), Aronix M-140, M-215, M-350 (products of Toagosei), NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG, and HD-N (products of Shin-Nakamura Kagaku Kogyosha).

Among these, mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups, and esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols are suitable for the alkaline-developable photosensitive resin composition of the present invention.

Ethylenically unsaturated compounds can be used alone or in combination of two or more, and when two or more are used in combination, they can be copolymerized in advance and used as a copolymer.

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

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; anthanthrone compounds; perinone compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, Ketchen black or lamp black; The carbon black above is adjusted or coated with an epoxy resin, the carbon black is dispersed in a resin in advance in a solvent and 20 to 200 mg/g of the resin is adsorbed, the carbon black is surface-treated with acid or alkali, the average particle size is 8 nm or more and the DBP absorption is 90 ml/100 g or less, the total oxygen content calculated from CO and _CO2 in the volatile matter at 950°C is 9 mg or more per 100 ^m2 of the surface area of the carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; Organic or inorganic pigments such as chromium oxide green, millimeter blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate blue, prussian blue, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, yellow lead, zinc yellow, bengala (red iron (III) oxide), cadmium red, synthetic iron black, and umber can be used. These pigments can be used alone or in combination.

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

The dyes mentioned above include dyes such as azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes, 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, per 100 parts by mass of the ethylenically unsaturated compound (B).

The photosensitive composition of the present invention may further contain an alkaline developable compound (D) to form an alkaline developable photosensitive resin composition. A composition that simultaneously contains a colorant (C) and an alkaline developable compound (D) is also called a colored alkaline developable photosensitive resin composition.

The above alkaline developing compound (D) is not particularly limited as long as it is soluble in an alkaline aqueous solution, and examples thereof include resins described in Japanese Patent Application Laid-Open No. 2004-264414.

In addition, as the alkaline developing compound (D), a resin obtained by reacting an unsaturated monobasic acid on an epoxy group of an epoxy compound, such as a copolymer of an acrylic acid ester, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, an epoxy acrylate resin, a polymer having a carboxyl group, an epoxy compound represented by the following general formula (IV), and further reacting a polybasic anhydride can be used.

The above epoxy acrylate resin is a resin that has been produced by reacting (meth)acrylic acid with an epoxy compound, and examples thereof include Ripoxy SPC-2000, DickRite UE-777 manufactured by DIC Corporation, and Yupika 4015 manufactured by Nippon Yupika Corporation.

Among these compounds, epoxy acrylate resins and polymers having carboxyl groups are preferred.

The polymer having the above carboxyl group may have a structural unit having a carboxyl group (hereinafter referred to as “structural unit (U1)”), and is not particularly limited. The polymer having the above carboxyl group preferably has, in addition to the structural unit (U1), a structural unit having a crosslinking group such as a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, and an isocyanate group (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 the above carboxyl group may have a structural unit other than the structural units (U1) to (U3) (hereinafter referred to as “structural unit (U4)”).

It is preferable that the above structural unit (U1) is a structural unit derived from at least one compound (hereinafter referred to as “compound (u1)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

Examples of the above 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-methacryloyloxyethylhexahydrophthalic acid.

Examples of the above dicarboxylic acids include maleic acid, fumaric acid, and citraconic acid.

Anhydrides of the above dicarboxylic acids include anhydrides of the above dicarboxylic acids.

Among these compounds, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid or maleic anhydride are particularly preferable in terms of copolymerization reactivity and solubility of the resulting copolymer in a developer.

The polymer having the above carboxyl group may have one type of structural unit (U1) derived from one type of compound (u1), or may have two or more types of structural units (U1) derived from two or more types of compounds (u1).

It is preferable that the above structural unit (U2) is a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter referred to as “compound (u2)”).

It is preferable that the above compound (u2) is 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.

As polymerizable unsaturated compounds having an epoxy group, examples thereof include (meth)acrylic acid oxiranyl (cyclo) alkyl ester, α-alkylacrylic acid oxiranyl (cyclo) alkyl ester, and glycidyl ether compounds having a polymerizable unsaturated bond.

As a polymerizable unsaturated compound having an oxetanyl group, examples thereof include (meth)acrylic acid ester having an oxetanyl group.

Specific examples of (meth)acrylic acid oxiranyl (cyclo)alkyl esters include, for example, (meth)acrylic acid glycidyl, (meth)acrylic acid 2-methylglycidyl, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylic acid 3,4-epoxybutyl, (meth)acrylic acid 6,7-epoxyheptyl, (meth)acrylic acid 3,4-epoxycyclohexyl, (meth)acrylic acid 3,4-epoxycyclohexylmethyl, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate.

Specific examples of α-alkylacrylic acid oxiranyl(cyclo)alkyl esters include, for example, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butylacrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, and α-ethyl acrylate 3,4-epoxycyclohexyl.

Specific examples of glycidyl ether compounds having polymerizable unsaturated bonds 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, and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

Among these compounds, glycidyl methacrylate, 2-methyl glycidyl 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 ]decylacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane are particularly preferable from the viewpoint of polymerizability.

The polymer having the above carboxyl group may have one type of structural unit (U2) derived from one type of compound (u2), or may have two or more types of structural units (U2) derived from two or more types of compounds (u2).

Among the structural units (U2) above, a structural unit having a methacryloyl group or an acryloyl group as a crosslinking group can preferably be used, a structural unit having a (meth)acryloyloxy group.

The structural unit having the above (meth)acryloyloxy group is obtained by reacting a (meth)acrylic acid ester having an epoxy group with a carboxyl group in a polymer. The structural unit having the (meth)acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U).

(In the formula, 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),

* indicates a combination number.)

(In the formula, R ¹⁰⁰³ represents a hydrogen atom or a methyl group,

* indicates a combination number.)

For the structural unit represented by the above formula (U), for example, when a compound such as glycidyl methacrylate or 2-methyl glycidyl methacrylate is reacted with a copolymer having a carboxyl group, R ¹⁰⁰² in formula (U) becomes 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 of the unsaturated compound such as (meth)acrylic acid ester having a carboxyl group and an epoxy group in the polymer as described above is preferably carried out by adding the unsaturated compound having an epoxy group to a solution of the polymer, preferably including a polymerization inhibitor, in the presence of a suitable catalyst as needed, and stirring the solution under heating for a predetermined time. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol. The reaction temperature is preferably 70°C to 100°C. The reaction time is preferably 8 to 12 hours.

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

It is preferable that the above structural unit (U3) is a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter referred to as “compound (u3)”).

Examples of the compound (u3) include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane.

When the polymer having the above carboxyl group has the structural unit U3, it may have one type of structural unit (U3) derived from one type of compound (u3), or it may have two or more types of structural units (U3) derived from two or more types of compounds (u3).

The above structural unit (U4) is a structural unit other than the above (U1) to (U3), and is preferably a structural unit derived from a polymerizable unsaturated compound other than the above (u1) to (u3) (hereinafter referred to as “compound (u4)”).

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 having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds.

Specific examples of (meth)acrylic acid alkyl esters include methyl acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate.

Specific examples of (meth)acrylic acid cycloalkyl esters include, for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, 2-(tricyclo[5.2.1.0 ^2,6 ]decan-8-yloxy)ethyl (meth)acrylate, and isobornyl (meth)acrylate.

Specific examples of (meth)acrylic acid aryl esters include, for example, phenyl acrylate.

Specific examples of (meth)acrylic acid aralkyl esters include, for example, (meth)acrylic acid benzyl.

Specific examples of unsaturated dicarboxylic acid dialkyl esters include diethyl maleate, diethyl fumarate, etc.

Specific examples of (meth)acrylic acid esters having an oxygen-containing heterocyclic 5-membered ring or an oxygen-containing heterocyclic 6-membered ring include (meth)acrylic acid tetrahydrofuran-2-yl, (meth)acrylic acid tetrahydropyran-2-yl, and (meth)acrylic acid 2-methyltetrahydropyran-2-yl.

Specific examples of vinyl aromatic compounds include styrene, α-methylstyrene, etc.

Specific examples of conjugated diene compounds include, for example, 1,3-butadiene and isoprene.

Specific examples of other polymerizable unsaturated compounds include, for example, 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

Among the compounds (u4) mentioned above, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, and 1,3-butadiene are preferable in terms of copolymerization reactivity.

When the polymer having the above carboxyl group has a structural unit (U4), it may have one type of structural unit (U4) derived from one type of compound (u4), or it may have two or more types of structural units (U4) derived from two or more types of compounds (u4).

The polymer having a preferred carboxyl group in the present embodiment can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the compounds (u1) to (u4) described above in the following ratios.

In addition, by reacting a (meth)acrylic acid ester having an epoxy group with a carboxyl group among the structural units derived from compound (u1) in the obtained copolymer, it is possible to have a structural unit having a (meth)acryloyloxy group.

Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, and even more preferably 5 mol% to 15 mol%

Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 30 mol%

Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, and even more preferably 10 mol% to 30 mol%

Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, and even 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 is preferable because it achieves high resolution without compromising good coatability, and thus a cured film with highly adjusted physical property balance can be obtained even in a high-definition pattern.

The weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. By using a polymer having a carboxyl group having an Mw in this range, high resolution is achieved without compromising good coatability, so that even with a high-definition pattern, a cured film with highly adjusted balance of properties can be provided.

In the present invention, the weight average molecular weight (Mw) refers to the weight average molecular weight (Mw) converted to polystyrene as measured by gel permeation chromatography (GPC).

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

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

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

Among the polymers having the above carboxyl group, a polymer described in Japanese Patent Application Laid-Open No. 2005-234362 and a polymer obtained by reacting an unsaturated monobasic acid on an epoxy group of an epoxy compound represented by the following general formula (VI) and further reacting a polybasic acid anhydride are preferable.

In addition, as the alkaline-developable compound (D), a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound, such as a copolymer of an acrylic acid ester, a phenol and/or cresol novolac epoxy resin, a polyphenylmethane-type epoxy resin having a polyfunctional epoxy group, an epoxy acrylate resin, an epoxy compound represented by the following general formula (III), and further reacting a polybasic acid anhydride can be used. The epoxy acrylate resin referred to here is one in which (meth)acrylic acid is reacted with the epoxy compound, and examples thereof include Ripoxy SPC-2000, DickRite UE-777 manufactured by DIC, and Yupika 4015 manufactured by Nippon Yupika.

Among these, epoxy acrylate resins and resins obtained by reacting an unsaturated monobasic acid on the epoxy group of an epoxy compound represented by the following general formula (IV) and further reacting a polybasic acid anhydride are preferable.

In addition, it is preferable that the compound having alkaline developability and having the above-mentioned ethylenically unsaturated bond contains 0.2 to 1.0 equivalents of an unsaturated group.

(In the formula, X ²¹ represents 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 〔Formula (i)〕, 〔Formula (ii)〕, or 〔Formula (iii)〕, and the alkylidene group may be 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, and the alkyl group, alkoxy group, and alkenyl group may be substituted with a halogen atom,

In cases where R ⁵¹ and R ⁵² exist in multiples, 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 isomer that exists when m is not 0 can be any isomer.)

〔Formula (i)〕

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

〔Formula (ii)〕

(In the formula, * indicates the number of combinations.)

〔Formula (iii)〕

(In the formula, Y ² and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, 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, an arylalkenyl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom, and a methylene group in the group represented by Y ² may be substituted with an unsaturated bond, -O- or -S-, Z ² may form a ring with adjacent Z ² , and f is 0 to 4. represents an integer, g represents an integer from 0 to 8, h represents an integer from 0 to 4, i represents an integer from 0 to 4, the sum of the numbers of h and i is an integer from 2 to 4, and * represents a combined number.)

The unsaturated monobasic acids that can be used to react with the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate, and the like.

The polybasic acid anhydrides to be reacted after the unsaturated monobasic acid is reacted include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride. Examples include phthalic anhydride-maleic anhydride adducts, dodecenyl succinic anhydride, and methyl succinic anhydride.

It is preferable that the reaction molar ratio of the above epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride be as follows.

That is, it is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride per hydroxyl group of the epoxy adduct, which has 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, is 0.1 to 1.0.

The reaction of the above epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.

One embodiment of the photosensitive composition of the present invention, the alkaline developable photosensitive resin composition of the present invention, contains a photopolymerization initiator (A), an ethylenically unsaturated compound (B), and an alkaline developable compound (D) as essential components, and contains a combination of components such as an inorganic compound and a solvent as optional components. Meanwhile, among the alkaline developable photosensitive resin compositions of the present invention, those containing a colorant (C) are also referred to as, in particular, a colored alkaline developable photosensitive resin composition of the present invention.

The above alkaline developing compound (D) may be used alone or in combination of two or more types.

When the alkaline developable compound (D) above has an ethylenically unsaturated bond, the alkaline developable compound (D) may fall within the category of an ethylenically unsaturated compound (B). When the alkaline developable compound (D) is also an ethylenically unsaturated compound (B), a composition containing the alkaline developable compound (D) is a photosensitive composition and is also an alkaline developable photosensitive resin composition.

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

The above 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, Examples thereof include 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 monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, and compounds No. A2 and No. A3 above.

It is preferable to use at least one compound selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers as the above-mentioned multifunctional epoxy compound, since a (colored) alkaline-developable photosensitive resin composition having even better characteristics can be obtained.

In addition to the epoxy compound represented by the general formula (IV) that can be used as the above bisphenol-type epoxy compound, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used.

In addition, the above 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, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, 1,1,1,1-Tetra(glycidyloxymethyl)methane, etc. can be used.

In addition, novolac-type epoxy compounds such as phenol novolac-type epoxy compounds, biphenyl novolac-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol A novolac-type epoxy compounds, and dicyclopentadiene novolac-type epoxy compounds; alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester; glycidyl amines 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; dicyclopentadiene-type epoxy compounds, etc. can also be used.

In particular, when the photosensitive composition of the present invention is an alkali-developable photosensitive resin composition, the content of the compound having alkali-developability which may have an ethylenically unsaturated bond is preferably 1 to 20 mass%, particularly preferably 3 to 12 mass%, in the alkali-developable photosensitive resin composition of the present invention.

The photosensitive composition of the present invention may further contain a solvent. As the solvent, a solvent capable of dissolving or dispersing each of the above components (photopolymerization initiator (A) and ethylenically unsaturated compound (B), etc.) as necessary, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; Examples thereof include paraffin solvents such as mineral spirits, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 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); N-methylpyrrolidone; dimethyl sulfoxide; and water. These solvents can be used alone or as a mixture of two or more.

Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are preferable because they have good compatibility with the resist and the photopolymerization initiator (A) in the photosensitive composition.

In addition, the photosensitive composition of the present invention may contain, as needed, conventional additives such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; antifoamers; leveling agents; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-coagulants; catalysts; effect promoters; crosslinking agents; and thickeners.

The photosensitive composition of the present invention may include a dispersant that disperses the colorant (C) and/or the inorganic compound. The dispersant is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and commercially available dispersants, for example, BYK series products of BYK Chemie Japan, can be used. In particular, a polymer dispersant composed of polyester, polyether, or polyurethane having a basic functional group, a polymer dispersant having a nitrogen atom as the basic functional group, wherein the functional group having the nitrogen atom is an amine, and/or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH/g is suitably used.

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

(In the formula, ring A ¹ is a 6-membered alicyclic ring, aromatic ring or heterocyclic ring, and R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or -OR ⁶⁶ ,

At least one of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is not a hydrogen atom,

R ⁸⁶ represents 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, a heterocyclic group having 2 to 20 carbon atoms, or a trialkylsilyl group.)

(In the formula, ring A ¹ and R ⁹¹ are the same as the general formula (A) above,

X ⁷ is a group represented by the following general formula (1), and R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms, and at least one of R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ is not a hydrogen atom.)

(In the above general formula (1), X ⁸ represents -CR ⁹⁷ R ⁹⁸ -, -NR ⁹⁹ -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, or one of the substituents represented by the following 〔Formula (iv)〕 to 〔Formula (vi)〕,

Among the above aliphatic hydrocarbon groups, the methylene group may be substituted with -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a bonding group in which the oxygen atoms are not adjacent to each other and are combined with these.

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, Z ⁵ and Z ⁶ each independently represent a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO-, or >NR ¹⁰⁰ , R ⁹⁹ and R ¹⁰⁰ represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and * represents the number of bonds.)

〔Formula (iv)〕

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

〔Formula (v)〕

(In the formula, * indicates the number of combinations.)

〔Formula (vi)〕

(In the above formulas, R ¹⁰³ and R ¹⁰⁴ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, an arylalkenyl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, or a halogen atom, and the methylene group in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and R ¹⁰³ may form a ring with adjacent R ^103s , b represents a number of 0 to 4, c represents a number of 0 to 8, and g represents represents a number from 0 to 4, h represents a number from 0 to 4, and the sum of the numbers of g and h is 2 to 4.)

(wherein k=2~6, and X ⁹ is a group represented by the general formula (2) above when k=2, a group represented by the general formula (3) below when k=3, a group represented by the general formula (4) below when k=4, a group represented by the general formula (5) below when k=5, and a group represented by the general formula (6) below when k=6, and R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1~40 carbon atoms which may have a substituent, an aryl group having 6~20 carbon atoms, an arylalkyl group having 7~20 carbon atoms or a heterocycle-containing group having 2~20 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 is identical to the general formula (A) above.)

(In the above general formula (2), Y ¹¹ represents an aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and Z ¹¹ , Z ¹² and Z ¹³ each independently represent a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO-, -NR ¹²¹ -, -PR ¹²¹ -, or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent,

R ¹²¹ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and a methylene group in the aliphatic hydrocarbon group may be substituted with a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O- or -SO ₂ -.)

(In the above general formula (3), Y ¹² represents a carbon atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and a methylene group in the above aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and Z ¹¹ to Z ¹⁴ are each independently a group within the same range as the group represented by Z ¹¹ to Z ¹³ in the above general formula (2).)

(In the general formula (4) above, Y ¹³ represents an aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms, and the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and Z ¹¹ to Z ¹⁵ are each independently a group within the same range as the group represented by Z ¹¹ to Z ¹³ in the general formula (2).)

(In the general formula (5) above, Y ¹⁴ represents an aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and Z ¹¹ to Z ¹⁶ are each independently a group within the same range as the group represented by Z ¹¹ to Z ¹³ in the general formula (2).)

By using the above organic polymer [excluding the ethylenically unsaturated compound (B)], the properties of the cured product can also 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 polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like, and among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable.

When using an organic polymer, the amount used is preferably 10 to 500 parts by mass per 100 parts by mass of the polymerizable compound having the ethylenically unsaturated bond.

As the above chain transfer agent or the above sensitizer, a sulfur atom-containing compound is generally used. 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, Mercapto compounds such as mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), disulfide compounds obtained by oxidizing the above mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, iodide alkyl compounds such as trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following Compound No. C1, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, and other aliphatic polyfunctional thiol compounds, Showa Denko products Karenz MT BD1, PE1, NR1, etc.

As the above surfactants, fluorine-based surfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; cationic surfactants such as higher amine halogenates 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-based surfactants, etc., can be used, and these may be used in combination.

As the above silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, a silane coupling agent having an isocyanate group, an acryloyl group, a methacryloyl group, or an epoxy group such as KBE-9007, KBM-5103, KBM-502, or KBE-403 is suitably used.

The above melamine compounds include compounds in which all or part (at least two) of the active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea are alkyl etherified.

Here, the alkyl group constituting the alkyl ether may include a methyl group, an ethyl group, or a butyl group, and may be the same or different from each other. In addition, the methylol group that is not alkyl etherified may be self-condensed within one molecule, or may be condensed between two molecules, resulting in the formation of an oligomer component.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used. Among these, alkyl etherified melamine such as hexamethoxymethylmelamine and hexabutoxymethylmelamine is preferable.

As for the above leveling agent, if it has a leveling effect, an existing leveling agent can be used, and among them, a silicone-based leveling agent and a fluorine-based leveling agent are particularly preferably used.

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

As the above fluorine-based leveling agent, a commercially available fluorine-based leveling agent can be used, for example, Optul DSX, Optul DAC-HP (all products of Daikin Kogyo); Surfron S-242, Surfron S-243, Surfron S-420, Surfron S-611, Surfron S-651, Surfron S-386 (all products of AGC Seimi Chemical); BYK-340 (product of Big Chemie Japan); AC110a, AC100a (all products of AlginChemie); Megapack F-114, Megapack F-410, Megapack F-444, Megapack EXPTP-2066, Megapack F-430, Megapack F-472SF, Megapack F-477, Megapack F-552, Megapack F-553, Megapack F-554, Megapack F-555, Megapack R-94, Megapack RS-72-K, Megapack RS-75, Megapack F-556, Megapack EXPTF-1367, Megapack EXPTF-1437, Megapack F-558, Megapack EXPTF-1537 (all, DIC products); FC-4430, FC-4432 (all, Sumitomo 3M products); Commercially available products such as Ptagent 100, Ptagent 100C, Ptagent 110, Ptagent 150, Ptagent 150CH, Ptagent A-K, Ptagent 501, Ptagent 250, Ptagent 251, Ptagent 222F, Ptagent 208G, Ptagent 300, Ptagent 310, Ptagent 400SW (all Neos products); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, PF-3320 (all Kitamura Kagaku Sangyo products) can be used.

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

The photosensitive composition, alkaline-developable photosensitive resin composition or cured product of the present invention is a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; a color filter in a liquid crystal display element of color display of a display device (a color TV, a PC monitor, a portable information terminal, a digital camera, etc.); a color filter of a CCD image sensor; an electrode material for a plasma display panel; a powder coating; a printing ink; a printing plate; an adhesive; a dental composition; a gel coat; a photoresist for electronics; an electroplating resist; an etching resist; a dry film; a soldering resist; a resist for forming a configuration of various display devices; a composition for sealing electric and electronic components; a soldering resist; a magnetic recording material; a micromechanical component; a waveguide; an optical switch; a plating mask; an etching mask; a color test system; a glass fiber cable coating; a stencil for screen printing; a material for manufacturing a three-dimensional object by stereolithography; a material for holographic recording; an image recording material; a microelectronic circuit; a decolorizing material; It can be used for various purposes such as a decolorizing material for an image recording material; a decolorizing material for an image recording material using microcapsules; a photoresist material for a printed wiring board; a photoresist material for a UV and visible laser direct imaging system; a photoresist material or protective film used for forming a dielectric layer in sequential lamination of a printed circuit board, and there are no particular limitations on its use.

The photosensitive composition or the alkaline developable photosensitive resin composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for the purpose of forming a protrusion for a vertically aligned liquid crystal display element. It is particularly useful as a photosensitive composition for simultaneously forming a protrusion and a spacer for a vertically aligned liquid crystal display element.

The curing method of the photosensitive composition or the alkaline developable photosensitive resin composition of the present invention is described in detail below.

The photosensitive composition or the alkaline-developable photosensitive resin composition of the present invention can be applied onto a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, etc. by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, immersion, etc. In addition, after once being applied onto a support substrate such as a film, it can also be transferred onto another support substrate, and there is no limitation on the application method.

In addition, as a light source of energy rays used when curing the photosensitive composition of the alkaline developable photosensitive resin composition of the present invention, electromagnetic wave energy having a wavelength of 2000 to 7000 angstroms obtained from an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, a germicidal lamp, a light-emitting diode, a CRT light source, etc., or high energy rays such as electron rays, X-rays, and radiation can be used, and preferably, ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, and xenon arc lamps that emit light having a wavelength of 300 to 450 nm can be exemplified.

Furthermore, since the laser direct drawing method, which forms an image directly from digital information such as a computer without using a mask by using laser light as an exposure light source, can improve not only productivity but also resolution and positional accuracy, it is useful, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, but also excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, and YAG lasers that emit light in the visible to infrared range are also used. When these lasers are used, a sensitizing dye that absorbs the above-mentioned range from visible to infrared is added.

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

The photosensitive composition of the present invention, to which an ink repellent agent is added, is useful as a resin composition for forming a barrier rib for an inkjet method, and the composition is used for a color filter, and is particularly preferably used for a barrier rib for an inkjet method color filter having a profile angle of 50° or more. As the ink repellent agent, a fluorinated surfactant and a composition comprising a fluorinated surfactant are suitably used.

An optical element is manufactured by a method in which a partition formed by the photosensitive composition of the present invention partitions an image of a transfer target and an image area is formed by applying droplets to a concave portion of the partitioned transfer target by an inkjet method. At this time, it is preferable that the droplets contain a coloring agent and the image area is colored, and an optical element manufactured by the above method for manufacturing an optical element, which has at least a pixel group formed of a plurality of colored areas on a substrate and a partition that separates each colored area of the pixel group, is preferably used.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

〔Examples 1-1 to 1-3〕 Preparation of compound No. 1

[Example 1-1] Preparation of intermediate 1A (ketone compound)

Triphenylamine (3.3 g) and dichloroethane (15 g) were added to a four-necked flask, and aluminum chloride (5.8 g) and acetyl chloride (3.3 g) were added under ice cooling. After stirring at room temperature for 3 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid, stirred, and oil and water were separated. The organic layer was washed twice with a 5% HCl aqueous solution, and then additionally washed four times. The product layer was desolvated, purified by a silica gel column (hexane/ethyl acetate = 65/35), and intermediate 1A was obtained (2.6 g: yield 52%).

[Example 1-2] Preparation of intermediate 1B (oxime compound)

Intermediate 1A (2.6 g), ethanol (24 g), water (12 g), and hydroxylamine hydrochloride (1.6 g) were added to a four-necked flask, and heated and refluxed for 10 hours. After cooling to room temperature, the precipitate was filtered and extracted, and thoroughly dried to obtain intermediate 1B (2.8 g: yield 96%).

[Example 1-3] Preparation of compound No. 1 (oxime ester compound of the present invention)

Intermediate 1B (2.1 g) and dimethylformamide (15 g) were added to a four-necked flask, followed by adding triethylamine (1.7 g) and acetyl chloride (1.3 g) under ice cooling. After stirring at room temperature for 2 hours, ion-exchanged water (15 g) and ethyl acetate (30 g) were added, and oil and water were separated. The organic layer was washed three times, and after desolvation, it was purified by a silica gel column (hexane/ethyl acetate = 50/50) to obtain compound No. 1 (1.4 g: yield 50%). The NMR data of the obtained compound No. 1 are shown in [Table 1].

〔Examples 2-1 to 2-3〕Preparation of compound No. 2

[Example 2-1] Preparation of intermediate 2A (ketone compound)

Triphenylamine (5.9 g) and dichloroethane (40 g) were charged into a four-necked flask, and then aluminum chloride (10.5 g) and propionyl chloride (7.1 g) were added under ice cooling. After stirring at room temperature for 5 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid, stirred, and oil and water were separated. The organic layer was washed twice with a 5% HCl aqueous solution, and further washed four times with water. After desolvation of the product layer, purification was performed by a silica gel column (hexane/ethyl acetate = 80/20) to obtain intermediate 2A (3.9 g: yield 39%).

[Example 2-2] Preparation of intermediate 2B (oxime compound)

Intermediate 2A (3.9 g) and dimethylformamide (24 g) were weighed in a 4-necked flask, and under ice cooling, 35% hydrochloric acid (3.9 g) and isobutyl nitrite (3.9 g) were added dropwise, and stirred at room temperature for 20 hours. Ion-exchanged water (24 g) and ethyl acetate (48 g) were added, oil and water were separated, and the organic layer was washed three times. After desolvation of the organic layer, intermediate NCIx175-b was obtained (4.5 g: yield 96%).

[Example 2-3] Preparation of compound No. 2 (oxime ester compound of the present invention)

Intermediate 2B (4.5 g) and tetrahydrofuran (23 g) were placed in a 4-necked NASF, and under ice cooling, triethylamine (3.0 g) and acetyl chloride (2.2 g) were added dropwise in that order, and the mixture was stirred at room temperature for 2 hours. After adding ion-exchange water (17 g) and ethyl acetate (46 g), oil and water were separated, and the organic layer was washed 5 times. After desolvation of the organic layer, purification was performed using a silica gel column (hexane/ethyl acetate = 50:50) to obtain compound No. 2 (2.7 g: yield 48%). The NMR data of the obtained compound No. 2 are shown in [Table 1].

〔Examples 3-1 to 3-4〕Preparation of compound No. 133

[Example 3-1] Preparation of intermediate 133A

In a four-necked flask, fluorobenzene (27.7 g) and dichloroethane (192 g) were added, and then aluminum chloride (40.4 g) and n-octanoyl chloride (46.8 g) were sequentially added under ice cooling. After the reaction was performed at room temperature for 1 hour, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid, stirred, and separated into oil and water. The organic layer was washed twice with 5% diluted hydrochloric acid and three times with ion-exchanged 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), and dimethyl sulfoxide (133 g) were added to 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 three times, desolvated, and intermediate 133B was obtained (41.2 g: yield 93%).

[Example 3-3] Preparation of intermediate 133C (ketone compound)

Intermediate 133B (41.2 g) and dichloroethane (209 g) were added to a 4-necked flask, and then aluminum chloride (49.1 g) and n-octanoyl chloride (39.9 g) were sequentially added under ice cooling. After the reaction was performed at the same temperature for 4 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid, stirred, and separated into oil and water. The organic layer was washed twice with 5% diluted hydrochloric acid and three times with ion-exchanged water, and then desolvated to obtain intermediate 133C (50.5 g: 73%).

[Example 3-4] Preparation of compound No. 133 (oxime ester compound)

Intermediate 133C (10.0 g), dimethylformamide (50 g), hydroxylamine hydrochloride (3.7 g), and pyridine (4.2 g) were added to a four-necked flask, and the mixture was stirred at 80°C for 10 hours. After cooling with ice cooling, 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). The organic layer was washed three times, desolvated, and purified by a silica gel column (ethyl acetate/hexane = 1/4) to obtain compound No. 133 (2.3 g: yield 18%). The NMR data of the obtained compound No. 133 are shown in [Table 1].

〔Examples 4-1 to 4-2〕 Preparation of compound No. 134

[Example 4-1] Preparation of intermediate 134A (oxime compound)

Intermediate 133C (10.0 g) and DMF (10.0 g) were weighed in a 4-necked flask, and 35% hydrochloric acid (6.70 g) and isobutyl nitrite (6.63 g) were added dropwise under ice cooling, and stirred at room temperature for 20 hours. Ion-exchanged water (22.8 g) and ethyl acetate (34.2 g) were added, oil and water were separated, and the organic layer was washed three times. After desolvation of 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] Preparation of compound No. 134 (oxime ester compound)

Intermediate 134A (2.7 g) and ethyl acetate (10 g) were placed in a 4-necked NASF. Under ice cooling, triethylamine (1.3 g) and acetyl chloride (1.0 g) were sequentially added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. After adding ion-exchange water (12 g), oil and water were separated, and the organic layer was washed 5 times. After desolvation of the organic layer, purification was performed using a silica gel column (hexane/ethyl acetate = 85:15) to obtain compound No. 134 (0.89 g: yield 27%). The NMR data of the obtained compound No. 134 are shown in [Table 1].

[Manufacturing Example 1] Manufacturing of Blue Pigment Dispersion No. 1

A blue pigment dispersion was prepared by dispersing DISPERBYK-161 (12.5 parts by mass; a product of Big Chemie Japan) as a dispersant and Pigment Blue 15:6 (15 parts by mass) as a colorant in PGMEA (72.5 parts by mass) using a bead mill.

[Examples 5 to 7 and Comparative Examples 1 to 2] Preparation of photosensitive composition

Each component was prepared according to the proportions in [Table 2] and [Table 3], and photosensitive compositions No. 1 to 3 and comparative photosensitive compositions No. 1 to 2 were obtained. Meanwhile, numbers in the table represent parts by mass. Compounds No. 2, No. 133, No. 134, No. A2-3, and No. A2-11 were used alone as photopolymerization initiators.

Additionally, 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; Showa Denko product)

B-2: Kayarad DPHA (ethylenically unsaturated compound; Nippon Kayaku product)

C-1: Blue pigment dispersion No.1 (colorant PGMEA dispersion)

D-1: KBE-403 (silane coupling agent; Shin-Etsu Chemical Co., Ltd.)

D-2: F-554 (Oligomer containing fluorine and lipophilic group; DIC product)

E-1: PGMEA (solvent)

*SPC-3000 is an ethylenically unsaturated compound (B) and also an alkaline developing compound (D).

[Evaluation of cured product obtained from photosensitive composition]

The evaluation of brightness in the cured products obtained from the above photosensitive compositions No. 1 to 3 and the comparative photosensitive compositions No. 1 to 2 was performed in the following order. The results are shown in [Table 4].

(Brightness)

The photosensitive compositions No. 1 to 3 and the comparative photosensitive compositions No. 1 to 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, prebaked at 90°C for 90 seconds using a hot plate, and cooled at 23°C for 40 seconds. Thereafter, 100 mJ/cm2 was irradiated using a high-pressure mercury lamp to produce an evaluation sample. The Y value was obtained in accordance with JIS Z8701 from the transmittance of the obtained sample at 380 to 780 nm. A sample having a Y value of 9.5 or more was designated as A, and a sample having a Y value of less than 9.5 was designated as B. A higher BY value means higher luminance and is useful. A sample having a luminance evaluation of A can be preferably used for a color filter, and a sample having an evaluation of B is not suitable for a color filter.

[Evaluation of photosensitive compositions]

In the above luminance evaluation, the sensitivity evaluation of the photosensitive compositions No. 1, 3, and comparative photosensitive composition No. 1, which were evaluated as A, was performed in the following order. The results are shown in [Table 5].

(sensitivity)

The photosensitive compositions No. 1 to 3 and the comparative photosensitive compositions No. 1 to 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, prebaked at 90°C for 90 seconds using a hot plate, and cooled at 23°C for 40 seconds. Thereafter, exposure was performed through a mask using a high-pressure mercury lamp. A 2.5 mass%<sodium carbonate aqueous solution was used as a developer, and after development, the result was thoroughly washed, post-baked at 230°C for 30 minutes using an oven, and the pattern was fixed. The pattern for an exposure dose of 40 mJ/cm2 was observed with an electron microscope, and the line width at a mask opening of 30 μm was measured. A line width of 35 μm or more was designated as A, a line width of 25 μm or more was designated as B, and a line width of less than 25 μm was designated as C. The larger the line width, the better the sensitivity. Photosensitive compositions having sensitivity evaluations of A and B can be used for color filter purposes, and a photosensitive composition having sensitivity evaluation of A is particularly preferred. A photosensitive composition having sensitivity evaluation of C is not suitable for color filter purposes.

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

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

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

Claims (9)

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

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

(In the formula, R ³¹ and R ³² each independently represent a hydrocarbon group having 1 to 20 carbon atoms,
n represents 1, and * represents a combination number.) A photopolymerization initiator containing the oxime ester compound described in claim 1. A photosensitive composition containing the photopolymerization initiator (A) and the ethylenically unsaturated compound (B) described in claim 2. In the third paragraph,
A photosensitive composition additionally containing a colorant (C). An alkaline-developable photosensitive resin composition containing the photosensitive composition described in claim 3 and an alkaline-developable compound (D). A cured product of the photosensitive composition described in claim 3 or claim 4 or the alkaline developable photosensitive resin composition described in claim 5. A display device containing the cured product described in Article 6. A method for producing a cured product, comprising a process of curing the photosensitive composition described in claim 3 or claim 4 or the alkaline developable photosensitive resin composition described in claim 5 by light irradiation or heating. delete