JP2023097940A - photosensitive composition - Google Patents

Abstract

To provide a photosensitive composition that can be sufficiently cured even when containing titanium nitride and/or titanium oxynitride as a colorant, a method for producing a patterned cured film using the photosensitive composition, and a patterned cured film including a cured product of the photosensitive composition.SOLUTION: A photosensitive composition contains an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light blocker (D) including titanium nitride and/or titanium oxynitride. The photopolymerization initiator (C) includes a combination of an oxime ester compound (C1) with at least one compound (C2) selected from phosphine oxide compounds (C2a) and amino ketone compounds (C2b).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a photosensitive composition, a method for producing a patterned cured film using the photosensitive composition, and a patterned cured film comprising a cured product of the photosensitive composition.

For example, in a display device such as a liquid crystal display device, a large number of light shielding members such as a black matrix are used. Such members are often formed as patterned films. In order to form a patterned film, a photosensitive composition that gives a cured film upon exposure is widely used. A patterned cured film can be formed by developing such a photosensitive composition after position-selectively exposing it.

For example, as a photosensitive composition capable of forming a light-shielding film such as a black matrix, disclosed is a photosensitive composition containing a coloring agent such as titanium nitride or titanium oxynitride, a polymerizable compound, and a photopolymerization initiator. (See the example of Patent Document 1).

Japanese Patent Application Laid-Open No. 2021-12389

However, when using a photosensitive composition containing a coloring agent such as titanium nitride or titanium oxynitride, it is often difficult to cure the photosensitive composition satisfactorily.

The present invention has been made in view of the above problems, and includes a photosensitive composition that cures satisfactorily even if it contains titanium nitride and/or titanium oxynitride as a coloring agent, and a photosensitive composition that uses the photosensitive composition. An object of the present invention is to provide a method for producing a patterned cured film, and a patterned cured film formed from a cured product of the photosensitive composition.

The present inventors have made intensive studies to achieve the above objects, and found that an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), titanium nitride, and/or Alternatively, in a photosensitive composition containing a light-shielding agent (D) containing titanium oxynitride, at least one selected from an oxime ester compound (C1) and a phosphine oxide compound (C2a) and an aminoketone compound (C2b) The present inventors have found that the above problems can be solved by using a photopolymerization initiator (C) containing the compound (C2) in combination, and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D). The photopolymerization initiator (C) comprises an oxime ester compound (C1) in combination with at least one compound (C2) selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b),
A light-shielding agent (D) is a photosensitive composition containing titanium nitride and/or titanium oxynitride.

A second aspect of the present invention is
Coating the photosensitive composition according to the first aspect on a substrate to form a coating film;
position-selectively exposing the coating film;
Developing the exposed coating film;
A method for producing a patterned cured film, comprising:

A third aspect of the present invention is a patterned cured film comprising a cured product of the photosensitive composition according to the first aspect.

INDUSTRIAL APPLICABILITY According to the present invention, a photosensitive composition that cures satisfactorily even if it contains titanium nitride and/or titanium oxynitride as a coloring agent, and a method for producing a patterned cured film using the photosensitive composition. and a patterned cured film made of a cured product of the photosensitive composition.

It is a schematic diagram which shows the cross-sectional shape of the width direction of the pattern formed using the photosensitive composition.

<<Photosensitive composition>>
The photosensitive composition contains an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D). The photopolymerization initiator (C) includes an oxime ester compound (C1) in combination with at least one compound (C2) selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b).
The light shielding agent (D) contains titanium nitride and/or titanium oxynitride.

The photosensitive composition contains an alkali-soluble resin (A), a photopolymerizable monomer (B), a coloring agent (D) containing titanium nitride and/or titanium oxynitride, and a photopolymerization initiator (C),
By containing the oxime ester compound (C1) in combination with at least one compound (C2) selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b), the photosensitive composition is cured satisfactorily. do.
As a result, the photosensitive composition can be used to form a cured product with excellent water resistance and to form a patterned cured film having a cross-sectional shape with a preferred taper angle.

The essential components and optional components contained in the photosensitive composition and the method for preparing the photosensitive composition will be described below in order.
<Alkali-soluble resin (A)>
The photosensitive composition contains an alkali-soluble resin (A) (hereinafter also referred to as component (A)). By blending the alkali-soluble resin (A) into the photosensitive composition, alkali developability can be imparted to the photosensitive composition.

In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and KOH having a concentration of 0.05% by mass. It is a material that dissolves at a film thickness of 0.01 μm or more when immersed in an aqueous solution for 1 minute.

Resins suitable as the alkali-soluble resin (A) include a resin (a-1) having a cardo structure (hereinafter also referred to as "cardo resin (a-1)").
When the resin (a-1) having a cardo structure is used as the alkali-soluble resin, it is easy to obtain a photosensitive composition having excellent resolution, and the photosensitive composition is used to form a cured film that is less likely to flow excessively when heated. Cheap. Therefore, it is easy to form a cured film having a good shape.

[Resin (a-1) having cardo structure]
As the resin (a-1) having a cardo skeleton, a resin having a cardo skeleton in its structure and having a predetermined alkali solubility can be used. A cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting a first ring structure. The second ring structure and the third ring structure may be the same structure or different structures.
A representative example of the cardo skeleton is a skeleton in which two aromatic rings (eg, benzene rings) are bonded to the 9-position carbon atom of a fluorene ring.

The cardo resin (a-1) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable.

In formula (a-1), X ^a represents a group represented by formula (a-2) below. m1 represents an integer of 0 or more and 20 or less.

In the above formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 each independently represents a hydrogen atom or a methyl group. R ^a3 each independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^a represents a group represented by the following formula (a-3).

In formula (a-2), R ^a3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 6 carbon atoms. is particularly preferred, and ethane-1,2-diyl, propane-1,2-diyl and propane-1,3-diyl groups are most preferred.

Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and which may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Aliphatic rings include monocycloalkanes, bicycloalkanes, tricycloalkanes, tetracycloalkanes and the like.
Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring which may be condensed with the aliphatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferred.

Suitable examples of the divalent group represented by formula (a-3) include the following groups.

The divalent group X ^a in the formula (a-1) can be obtained by reacting a tetracarboxylic dianhydride that gives the residue Z ^a with a diol compound represented by the following formula (a-2a). It is introduced into the resin (a-1).

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 and m2 are as described for formula (a-2). Ring A in formula (a-2a) is as described for formula (a-3).

A diol compound represented by formula (a-2a) can be produced, for example, by the following method.
First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is, if necessary, replaced by a group represented by —R ^a3 —OH according to a conventional method, Glycidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).
Then, the epoxy compound represented by formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by formula (a-2a).
In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 and m2 are as described for formula (a-2). Ring A in formulas (a-2b) and (a-2c) is as described for formula (a-3).
The method for producing the diol compound represented by formula (a-2a) is not limited to the above method.

Suitable examples of the diol compound represented by formula (a-2b) include the following diol compounds.

In formula (a-1) above, R ^a0 is a hydrogen atom or a group represented by —CO—Y ^a —COOH. Here, Y ^a represents a residue obtained by removing the acid anhydride group (--CO--O--CO--) from the dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride. Examples include phthalic anhydride and glutaric anhydride.

In the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. , biphenyl ether tetracarboxylic dianhydride, and the like.
In the above formula (a-1), m represents an integer of 0 or more and 20 or less.

（式（ａ－４）中、Ｒ^ａ４、Ｒ^ａ５、及びＲ^ａ６は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍ３は、０以上１２以下の整数を示す。）

(In formula (a-4), R ^a4 , R ^a5 , and R ^a6 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. and m3 is an integer from 0 to 12.)

The alkyl group that can be selected as R ^a4 in formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group within this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, even more preferably 1 or more and 4 or less, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. 1 or more and 3 or less are particularly preferable.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

R ^a4 in formula (a-4) is more preferably a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms independently from the viewpoint that a cardo resin having excellent heat resistance can be easily obtained. R ^a4 in formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, particularly preferably a hydrogen atom or a methyl group.
Plural R ^a4 groups in formula (a-4) are preferably the same group, since this facilitates the preparation of a highly pure tetracarboxylic dianhydride.

m3 in formula (a-4) represents an integer of 0 or more and 12 or less. By setting the value of m3 to 12 or less, purification of the tetracarboxylic dianhydride can be facilitated.
The upper limit of m3 is preferably 5, more preferably 3, from the viewpoint of facilitating purification of the tetracarboxylic dianhydride.
From the viewpoint of chemical stability of the tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, more preferably 2.
m3 in formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^a5 and R ^a6 in formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a4 .
R ^a5 and R ^a6 each have a hydrogen atom or a carbon atom number of 1 to 10 (preferably 1 to 6, more preferably 1 to 5, since purification of the tetracarboxylic dianhydride is easy, more preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less), and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″, 6,6''-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6'' -tetracarboxylic dianhydride”), methylnorbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-(methylnorbornane)-5,5″,6,6″-tetra Carboxylic acid dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (also known as "norbornane- 2-spiro-2′-cyclohexanone-6′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride”), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'- spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α′-spiro-2″-norbornane-5, 5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α′-spiro-2″-norbornane-5,5″,6,6′ '-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride , norbornane-2-spiro-α-cyclononanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone -α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2' '-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5' ',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''- tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α -(methylcyclopentanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone) -α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride and the like.

The weight average molecular weight of the cardo resin (a-1) is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 10,000. By setting the content within the above range, it is possible to obtain sufficient heat resistance and mechanical strength for a cured film formed using the photosensitive composition while obtaining good developability.

[Novolac resin (a-2)]
It is also preferable that the alkali-soluble resin (A) contains the novolac resin (a-2) from the viewpoint of easily forming a cured film that does not flow excessively when heated.
As the novolak resin (a-2), various novolak resins conventionally blended in photosensitive compositions can be used. As the novolak resin (a-2), those obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst are preferred.

(Phenols)
Phenols used for producing the novolak resin (a-2) include, for example, phenol; cresols such as o-cresol, m-cresol and p-cresol; 2,3-xylenol and 2,4-xylenol , 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, and other ethylphenols;2 -alkylphenols such as isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; 2,3,5-trimethylphenol and 3,4 ,5-trimethylphenol, etc.; polyhydric phenols, such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; alkyl polyhydric phenols, such as alkylresorcinol, alkylcatechol and alkylhydroquinone. (All alkyl groups have from 1 to 4 carbon atoms.); α-naphthol; β-naphthol; hydroxydiphenyl; These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferred, and the combined use of m-cresol and p-cresol is more preferred. In this case, various properties such as heat resistance of the cured film formed using the photosensitive composition can be adjusted by adjusting the mixing ratio of both.
The mixing ratio of m-cresol and p-cresol is not particularly limited, but the molar ratio of m-cresol/p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in such a ratio, it is easy to obtain a photosensitive composition capable of forming a cured film having excellent heat resistance.

Also preferred is a novolac resin produced by using m-cresol and 2,3,5-trimethylphenol in combination. When such a novolac resin is used, it is particularly easy to obtain a photosensitive composition capable of forming a cured film having excellent heat resistance.
The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the molar ratio of m-cresol/2,3,5-trimethylphenol is 70/30 or more and 95/5 or less. is preferred.

(aldehydes)
Examples of aldehydes used in producing the novolac resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(acid catalyst)
Examples of acid catalysts used in producing the novolac resin (a-2) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfate, and organic acids such as p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(molecular weight)
The polystyrene-equivalent weight-average molecular weight (Mw; hereinafter also simply referred to as "weight-average molecular weight") of the novolak resin (a-2) is, from the viewpoint of heat resistance of a cured film formed using a photosensitive composition, The lower limit is preferably 2,000, more preferably 5,000, particularly preferably 10,000, more preferably 15,000, most preferably 20,000, and the upper limit is more preferably 50,000, more preferably 45,000, even more preferably 40,000, and most preferably 35,000.

As the novolac resin (a-2), at least two kinds of resins having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of different weight-average molecular weights, the developability of the photosensitive composition and the heat resistance of the cured film formed using the photosensitive composition can be balanced.

[Modified epoxy resin (a-3)]
The alkali-soluble resin (A) is a polybasic acid anhydride (a-3c) adduct (a-3) of a reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b). may contain Such an adduct is also referred to as "modified epoxy resin (a-3)".
In the specification and claims of the present application, a compound that corresponds to the above definition and does not correspond to the resin (a-1) having a cardo structure is referred to as a modified epoxy resin (a-3 ).

The epoxy compound (a-3a), unsaturated group-containing carboxylic acid (a-3b), and polybasic acid anhydride (a-3c) are described below.

<Epoxy compound (a-3a)>
The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound containing no aromatic group. Often aromatic epoxy compounds with aromatic groups are preferred.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a polyfunctional epoxy compound having a functionality of two or more, and is preferably a polyfunctional epoxy compound.

Specific examples of the epoxy compound (a-3a) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin. functional epoxy resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; Glycidylamine type epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanurate; (2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4- [1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy] trifunctional epoxy resins such as 2-propanol; tetrafunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

As the epoxy compound (a-3a), an epoxy compound having a biphenyl skeleton is preferable.
The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in its main chain.
The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups.
By using an epoxy compound having a biphenyl skeleton, it is easy to obtain a photosensitive composition which is excellent in balance between sensitivity and developability and capable of forming a cured film excellent in adhesion to a substrate.

（式（ａ－３ａ－１）中、Ｒ^ａ７は、それぞれ独立に、水素原子、炭素原子数１以上１２以下のアルキル基、ハロゲン原子、又は置換基を有してもよいフェニル基であり、ｊは１以上４以下の整数である。）

(In formula (a-3a-1), each R ^a7 is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group, j is an integer of 1 or more and 4 or less.)

When R ^a7 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl. group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert- Octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl groups.

When R ^a7 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When R ^a7 is an optionally substituted phenyl group, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1.
Examples of substituents include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aliphatic acyl groups having 2 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups.

（式（ａ－３ａ－２）中、Ｒ^ａ７及びｊは、式（ａ－３ａ－１）と同様であり、ｋは括弧内の構成単位の平均繰り返し数であって０以上１０以下である。） The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, but examples thereof include epoxy compounds represented by the following formula (a-3a-2). be able to.

(In formula (a-3a-2), R ^a7 and j are the same as in formula (a-3a-1), and k is the average number of repetitions of the constituent units in the parentheses and is 0 or more and 10 or less. .)

（式（ａ－３ａ－３）中、ｋは、式（ａ－３ａ－２）と同様である。） Among the epoxy compounds represented by the formula (a-3a-2), it is particularly easy to obtain a photosensitive composition having an excellent balance between sensitivity and developability, so the epoxy compound represented by the following formula (a-3a-3) are preferred.

(In formula (a-3a-3), k is the same as in formula (a-3a-2).)

(Unsaturated group-containing carboxylic acid (a-3b))
In preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3b).
The unsaturated group-containing carboxylic acid (a-3b) is preferably a monocarboxylic acid containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, α-cyanocinnamic acid and cinnamic acid. Also, the unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more.

The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferred reaction method, for example, an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b) are reacted with a tertiary amine such as triethylamine or benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, Using a quaternary ammonium salt such as tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, triphenylphosphine, or the like as a catalyst, react in an organic solvent at a reaction temperature of 50° C. or higher and 150° C. or lower for several hours or more and several tens of hours or less. method.

In the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), the ratio of the amounts of both used is the epoxy equivalent of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid ( The ratio to the carboxylic acid equivalent of a-3b) is generally preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, and 1:0.9 to 1:1. .1 is particularly preferred.
When the ratio of the amount of the epoxy compound (a-3a) used and the amount of the unsaturated group-containing carboxylic acid (a-3b) used is 1:0.5 to 1:2 in terms of the above equivalent ratio, the crosslinking efficiency tends to improve, which is preferable.

(Polybasic acid anhydride (a-3c))
Polybasic anhydrides (a-3c) are anhydrides of carboxylic acids having two or more carboxyl groups.
The polybasic acid anhydride (a-3c) is not particularly limited, but examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydroanhydride. Phthalic acid, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexa Hydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride , a compound represented by the following formula (a-3c-1), and a compound represented by the following formula (a-3c-2). Also, the polybasic acid anhydride (a-3c) may be used alone or in combination of two or more.

（式（ａ－３ｃ－２）中、Ｒ^ａ８は、炭素原子数１以上１０以下の置換基を有してもよいアルキレン基を示す。）

(In formula (a-3c-2), R ^a8 represents an optionally substituted alkylene group having 1 to 10 carbon atoms.)

As the polybasic acid anhydride (a-3c), a compound having two or more benzene rings is preferable because it facilitates obtaining a photosensitive composition having an excellent balance between sensitivity and developability. In addition, the polybasic acid anhydride (a-3c) contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2). is more preferred.

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.
In addition, the ratio of the amount used is the number of moles of OH groups in the component after the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c ) is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it as the said range, it is easy to obtain the photosensitive composition with favorable developability.

The acid value of the modified epoxy resin (a-3) is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 110 mgKOH/g or less, in terms of resin solid content. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility in the developing solution can be obtained, and by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained, and surface properties can be improved. can be made better.

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1000 or more and 40000 or less, more preferably 2000 or more and 30000 or less. When the weight average molecular weight is 1000 or more, it is easy to form a cured film having excellent heat resistance and strength. Moreover, when it is 40,000 or less, it is easy to obtain a photosensitive composition exhibiting sufficient solubility in a developer.

[Acrylic resin (a-4)]
The acrylic resin (a-4) is also preferred as a component constituting the alkali-soluble resin (A).
As the acrylic resin (a-4), those containing structural units derived from (meth)acrylic acid and/or structural units derived from other monomers such as (meth)acrylic acid esters can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylic acid ester is represented by the following formula (a-4-1) and is not particularly limited as long as it does not interfere with the object of the present invention.

In formula (a-4-1) above, R ^a9 is a hydrogen atom or a methyl group, and R ^a10 is a monovalent organic group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. Moreover, this organic group may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic group of R ^a10 are not particularly limited as long as the effects of the present invention are not impaired, and include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, and cyanato groups. , isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkylthioether group, aryl ether group, arylthioether group, amino group (—NH ₂ , —NHR, —NRR′: R and R′ each independently represent a hydrocarbon group) and the like. A hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Moreover, the organic group as R ^a10 may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, or an oxetanyl group.
An acyl group having an unsaturated double bond or the like, such as an acryloyloxy group or a methacryloyloxy group, is, for example, an acrylic resin (a-4) containing a structural unit having an epoxy group. , and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.
In addition, an acyl group having an unsaturated double bond such as an acryloyloxy group or a methacryloyloxy group is at least part of the carboxy group in the acrylic resin (a-4) having a carboxy group and an unsaturated double bond. It can also be introduced into the acrylic resin (a-4) by reacting it with an epoxy compound having a bond.
As the epoxy compound having an unsaturated double bond, glycidyl (meth)acrylate, an alicyclic epoxy group-containing (meth)acrylic acid ester described later, or the like can be used.

R ^a10 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. Moreover, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec -pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group and the like.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl groups, , adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, and tetracyclododecyl group.

Specific examples of the compound represented by formula (a-4-1) when the compound represented by formula (a-4-1) has a chain group having an epoxy group as R ^a10 include: (Meth)acrylic acid epoxyalkyl esters such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. .

The compound represented by formula (a-4-1) may also be an alicyclic epoxy group-containing (meth)acrylic acid ester. The alicyclic group that constitutes the alicyclic epoxy group may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group etc. are mentioned as a polycyclic alicyclic group.

Specific examples of the case where the compound represented by formula (a-4-1) is an alicyclic epoxy group-containing (meth)acrylic acid ester include the following formulas (a-4-1a) to (a-4 -1o). Among these, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferable in order to obtain appropriate developability, and the following formulas (a-4-1a) to A compound represented by (a-4-1c) is more preferable.

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents 2 having 1 to 10 carbon atoms. represents a valent hydrocarbon group, and t represents an integer of 0 or more and 10 or less. R ^a21 is preferably a linear or branched alkylene group such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group and hexamethylene group. Examples of R ^a22 include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is phenylene group) is preferred.

Further, the acrylic resin (a-4) may be obtained by polymerizing a monomer other than the (meth)acrylic acid ester. Such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These monomers can be used alone or in combination of two or more.

(Meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N -methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide and the like.

Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; anhydrides of these dicarboxylic acids;

Allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; mentioned.

Vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether. , diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether , vinyl naphthyl ether, vinyl aryl ether such as vinyl anthranyl ether;

Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl Acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy alkylstyrenes such as methylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Halostyrenes such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene;

The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin (a-4) are not particularly limited as long as they do not hinder the object of the present invention. The amount of structural units derived from (meth)acrylic acid in the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less with respect to the mass of the acrylic resin (a-4), and 10 % by mass or more and 30% by mass or less is more preferable.

When the acrylic resin (a-4) has a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the acrylic resin (a-4) is 1% by mass or more. 50% by mass or less is preferable, 1% by mass or more and 30% by mass or less is more preferable, and 1% by mass or more and 20% by mass or less is particularly preferable.
Since the acrylic resin (a-4) contains a structural unit having an unsaturated double bond in the amount within the above range, the acrylic resin (a-4) is incorporated into the cross-linking reaction in the resist film and uniformly It is effective in improving the heat resistance and mechanical properties of the cured film.

The weight average molecular weight of the acrylic resin (a-4) is preferably 2000 or more and 50000 or less, more preferably 3000 or more and 30000 or less. By setting the amount within the above range, there is a tendency that the film-forming ability of the photosensitive composition and the developability after exposure are easily balanced.

The content of the alkali-soluble resin (A) in the photosensitive composition is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the solid content of the photosensitive composition. More than mass % and below 35 mass % are especially preferable. In addition, in this specification, solid content shows the sum total of components other than the solvent contained in the photosensitive composition.

<Photopolymerizable Monomer (B)>
The photopolymerizable monomer (B) (hereinafter also referred to as component (B)) contained in the photosensitive composition is not particularly limited, and conventionally known photopolymerizable monomers can be used. Among them, a monomer having an ethylenically unsaturated group is preferred.
Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers. The monofunctional monomer and the polyfunctional monomer will be described in order below.

Examples of monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N- Methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth)acrylate, half (meth)acrylate of phthalic acid derivative, and the like. These monofunctional monomers may be used alone or in combination of two or more.

Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3 - (meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin poly glycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, ( Polyfunctional monomers such as meth)acrylamidomethylene ether, condensates of polyhydric alcohols and N-methylol(meth)acrylamide, and triacrylformal. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer (B) in the photosensitive composition is preferably 3% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, based on the solid content of the photosensitive composition. 7% by mass or more and 20% by mass or less is particularly preferable.

<Photoinitiator (C)>
The photopolymerization initiator (C) (hereinafter also referred to as component (C)) is an oxime ester compound (C1), and at least one compound selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b). It contains the compound (C2) in combination.
The photopolymerization initiator (C) is a photopolymerization initiator other than the oxime ester compound (C1), the phosphine oxide compound (C2a), and the aminoketone compound (C2b), as long as the desired effect is not impaired. may contain

The photopolymerization initiator (C) is composed of the oxime ester compound (C1) and the phosphine oxide compound (C2a) in that it is easy to obtain the effect of using the oxime ester compound (C1) and the compound (C2) in combination. and an aminoketone-based compound (C2b) in combination.

The ratio of the mass of the compound (C2) to the sum of the mass of the oxime ester compound (C1) and the mass of the compound (C2) is, from the viewpoint of easily obtaining the desired effect based on good curing of the photosensitive composition, 10% by mass or more and 40% by mass or less is preferable, 12% by mass or more and 38% by mass or less is more preferable, and 15% by mass or more and 35% by mass or less is more preferable.

The oxime ester compound (C1), compound (C2), and other photopolymerization initiators are described in order below.

[Oxime ester compound (C1)]
As the oxime ester compound (C1), an oxime ester compound conventionally used as a photopolymerization initiator can be used without particular limitation.
In terms of the curability of the photopolymerization initiator, the oxime ester compound (C1) exhibits a gram absorption coefficient of 2.0 mL/g cm or more at a measurement wavelength of 405 nm when measured as a solution of propylene glycol monomethyl ether. It preferably contains an ester compound. The above gram extinction coefficient is more preferably 3.0 mL/g cm or more.
By including the oxime ester compound exhibiting the gram absorption coefficient as the oxime ester compound (C1) in the photosensitive composition, the photosensitive composition contains titanium nitride and/or titanium oxynitride as the light shielding agent (D). Even if it contains, the photosensitive composition cures satisfactorily.

As the oxime ester compound (C1), the following oxime ester compound (C1a) and oxime ester compound (C1b) are preferable.

（式（Ｃ１ａ）中、Ｘ^０１は、下記式（Ｃ１ａ－１）：

で表される構造において、芳香族環上に結合する水素原子のうち、ｔ２＋ｔ３個の水素原子を除いた基であり、Ｘ^０２及びＸ^０３は、それぞれ独立に１価の有機基であり、Ｘ^０４及びＸ^０５は、それぞれ独立に水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｔ０～ｔ３は、それぞれ独立に、０又は１であり、ｔ２及びｔ３の少なくとも一方は１であり、
式（Ｃ１ａ－１）中、Ｘ^０６は、カルバゾール環中の窒素原子にＣ－Ｎ結合で結合する１価の有機基であり、ｔ４及びｔ５は、それぞれ独立に０又は１であり、ｔ４及びｔ５の少なくとも一方は１である。） (Oxime ester compound (C1a))
The oxime ester compound (C1a) is a compound represented by the following formula (C1a).

(In formula (C1a), X ⁰¹ is the following formula (C1a-1):

In the structure represented by, of the hydrogen atoms bonded to the aromatic ring, a group excluding t2 + t3 hydrogen atoms, X ⁰² and X ⁰³ are each independently a monovalent organic group, and X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, and t0 to t3 are each independently 0 or 1, at least one of t2 and t3 is 1;
In formula (C1a-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring via a C—N bond, t4 and t5 are each independently 0 or 1, and t4 and At least one of t5 is 1. )

In formula (C1a-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring via a CN bond. The monovalent organic group may contain heteroatoms such as O, S, N, P, Si, and halogen atoms. The number of carbon atoms in the organic group as X ⁰⁶ is not particularly limited. The number of carbon atoms in the organic group as X ⁰⁶ is, for example, preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and particularly preferably 1 or more and 20 or less.

Preferred examples of organic groups as X ⁰⁶ include alkyl groups, alkenyl groups, alkynyl groups, aliphatic cyclic hydrocarbon groups, aryl groups, aliphatic heterocyclic groups, heteroaryl groups, aliphatic acyl groups, and aromatic acyl groups. groups, and combinations of these groups. Preferred examples of combinations of these groups include aralkyl groups and cycloalkylalkyl groups.

When the organic group as X ⁰⁶ is an alkyl group, alkenyl group, or alkynyl group, these groups may be linear or branched. When the organic group as X ⁰⁶ is an aliphatic acyl group, the portion other than the carbonyl group in the aliphatic acyl group may be linear, branched, or cyclic. , may be a combination of these structures.

The organic group as X ⁰⁶ may have a substituent. Examples of the substituent that the organic group represented by X ⁰⁶ may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 3 to 10 carbon atoms. cycloalkyl group, cycloalkoxy group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, saturated aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl group optionally having substituents, naphthoxy group optionally having substituents, naphthoyl group optionally having substituents, naphthoxycarbonyl group optionally having substituents, naphthoyl optionally having substituents oxy group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, optionally substituted heterocyclyl group, optionally substituted heterocyclylcarbonyl group, amino group, 1 , or amino group, morpholin-1-yl group and piperazin-1-yl group substituted with two organic groups, halogen, nitro group and cyano group.

Among the above groups for X ⁰⁶ , an alkyl group, an aryl group, and an aralkyl group are preferred in view of the ease of synthesis and availability of the oxime ester compound (C1a).

Specific examples of when X ⁰⁶ is an alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl group. , neopentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group. .

Preferable examples when X ⁰⁶ is an aryl group include a phenyl group, a naphthalen-1-yl group, a naphthalen-2-yl group, a 2-phenylphenyl group, a 3-phenylphenyl group and a 4-phenylphenyl group. is mentioned.

Preferred examples of X ⁰⁶ being an aralkyl group include benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, naphthalen-1-ylmethyl, and naphthalene-2 -ylmethyl group.

Among the specific examples of X ⁰⁶ explained above, a methyl group, an ethyl group, a phenyl group, a naphthalen-1-yl group and a naphthalen-2-yl group are preferable, and an ethyl group and a phenyl group are more preferable.

X ⁰¹ is not particularly limited as long as it is a group obtained by removing t2+t3 hydrogen atoms among the hydrogen atoms bonded to the aromatic ring in the structure represented by the above formula (C1a-1). As the group represented by the above formula (C1a-1), monovalent or divalent groups represented by the following formulas (C1a-1a) to (C1a-1c) are preferable.

In formulas (C1a-1a) to (C1a-1c), t4, t5 and ^X06 are the same as in formula (C1a-1). X ⁰⁷ is a divalent organic group attached to the nitrogen atom in the carbazole ring via a C—N bond. X ⁰⁷ is a divalent organic group containing an aromatic ring. Of the two bonds that X ⁰⁷ has, the other bond that bonds to the carbazole ring in formulas (C1a-1a) and (C1a-1c) bonds to the aromatic ring in X ⁰⁷ .
X ⁰⁷ corresponds to a divalent group obtained by removing one hydrogen atom bonded to the aromatic ring from the above-mentioned monovalent organic group containing an aromatic ring as X ⁰⁶ .

Taking formula (C1a-1a) as an example, preferred specific examples of X ⁰⁷ are described below. A divalent group corresponding to X ⁰⁷ in the structure below is also preferred as X ⁰⁷ in formula (C1a-1c).

In formulas (C1a-1a) to (C1a-1c), the bonding position of the nitro group on the carbazole ring is not particularly limited.
From the viewpoint of ease of synthesis and availability of the oxime ester compound (C1a), the group represented by the formula (C1a-1a), the group represented by the formula (C1a-1b), and the group represented by the formula (C1a-1c) Preferable examples of the group are represented by the formula (C1a-1aa), the group represented by the formula (C1a-1ba), and the group represented by the formula (C1a-1ca). .

In formula (C1a), X ⁰² and X ⁰³ are each independently a monovalent organic group. Examples of suitable organic groups for X ⁰² and X ⁰³ include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents. optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, substituted a naphthoxycarbonyl group optionally having a group, a naphthoyloxy group optionally having a substituent, a naphthylalkyl group optionally having a substituent, a heterocyclyl group optionally having a substituent, a substituent , an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like.

When X ⁰² and X ⁰³ are alkyl groups, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Also, when X ⁰² and X ⁰³ are alkyl groups, they may be linear or branched. Specific examples of X ⁰² and X ⁰³ being alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, Examples include isononyl group, n-decyl group, and isodecyl group. In addition, when X ⁰² and X ⁰³ are alkyl groups, the alkyl group may contain an ether bond (--O--) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.

When X ⁰² and X ⁰³ are alkoxy groups, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Moreover, when X ⁰² and X ⁰³ are alkoxy groups, they may be linear or branched. Specific examples where X ⁰² and X ⁰³ are alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy. group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec- Octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. Moreover, when X ⁰² and X ⁰³ are alkoxy groups, the alkoxy groups may contain an ether bond (--O--) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.

When X ⁰² and X ⁰³ are a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of X ⁰² and X ⁰³ being cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. When X ⁰² and X ⁰³ are cycloalkoxy groups, specific examples include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy groups. .

When X ⁰² and X ⁰³ are a saturated aliphatic acyl group or saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and 2 or more and 7 or less. more preferred. Specific examples of when R ^c7 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Noyl group, n-hexadecanoyl group and the like. Specific examples of when X ⁰² and X ⁰³ are saturated aliphatic acyloxy groups include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group and an n-pentanoyloxy group. , 2,2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When X ⁰² and X ⁰³ are alkoxycarbonyl groups, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when X ⁰² and X ⁰³ are alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n- heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, and the like.

When X ⁰² and X ⁰³ are phenylalkyl groups, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When X ⁰² and X ⁰³ are naphthylalkyl groups, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of X ⁰² and X ⁰³ being phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl groups. Specific examples of when X ⁰² and X ⁰³ are naphthylalkyl groups include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. is mentioned. When X ⁰² and X ⁰³ are a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or naphthyl group.

When X ⁰² and X ⁰³ are heterocyclyl groups, the heterocyclyl groups are 5- or 6-membered monocyclic rings containing one or more of N, S, O, or such monocyclic rings together, or such monocyclic rings and a benzene ring. is a fused heterocyclyl group. When the heterocyclyl group is a condensed ring, the condensed ring may have up to 3 monocyclic rings. A heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When X ⁰² and X ⁰³ are heterocyclylcarbonyl groups, heterocyclyl groups contained in the heterocyclylcarbonyl groups are the same as when X ⁰² and X ⁰³ are heterocyclyl groups.

When X ⁰² and X ⁰³ are an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cyclo group having 3 to 10 carbon atoms, Alkyl group, saturated aliphatic acyl group having 2 to 21 carbon atoms, phenyl group optionally having substituent(s), benzoyl group optionally having substituent(s), number of carbon atoms optionally having substituent(s) 7 to 20 phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthoyl groups, optionally substituted naphthylalkyl groups of 11 to 20 carbon atoms , and heterocyclyl groups. Specific examples of these suitable organic groups are the same as X ⁰² and X ⁰³ . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group and the like.

When the phenyl group, naphthyl group, and heterocyclyl group contained in X ⁰² and X ⁰³ further have a substituent, the substituent may be an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, alkoxy group, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 1 to 6 carbon atoms monoalkylamino group having an alkyl group, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group, etc. mentioned.

These substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, and a Alkoxycarbonyl group, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having alkyl group having 1 to 6 carbon atoms, and dialkylamino having alkyl group having 1 to 6 carbon atoms When it is a group, an ether bond (--O--) may be included in the carbon chain in these substituents.

When the phenyl group, naphthyl group, and heterocyclyl group contained in X ⁰² and X ⁰³ further have substituents, the number of the substituents is not limited as long as the object of the present invention is not impaired, but 1 or more and 4 or less. is preferred. When the phenyl group, naphthyl group and heterocyclyl group contained in X ⁰² and X ⁰³ have multiple substituents, the multiple substituents may be the same or different.

X ⁰² and X ⁰³ are also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are as described above as the substituents that the phenyl group may have.

Among the organic groups, X ⁰² and X ⁰³ are an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or an aromatic ring which may have a substituent. Good phenylthioalkyl groups are preferred. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, most preferably a methyl group. preferable. Among the optionally substituted phenyl groups, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferred.

As X ⁰² and X ⁰³ , a group represented by -A ¹ -CO-OA ² is also preferable. A ¹ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. ^A2 is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ¹ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ¹ is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Suitable examples of A ² include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Preferred specific examples of ^A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl. phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl groups.

Preferable specific examples of the group represented by -A ¹ -CO-OA ² include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n -butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, and 3-phenoxycarbonyl-n-propyl group.

式（Ｃ１ａ－ｉ）及び（Ｃ１ａ－ｉｉ）中、Ｘ^０８及びＸ^０９はそれぞれ有機基である。ｔ６は０以上４以下の整数である。Ｘ^０８及びＸ^０９がベンゼン環上の隣接する位置に存在する場合、Ｘ^０８及びＸ^０９が互いに結合して環を形成してもよい。ｔ７は１以上８以下の整数である。ｔ８は１以上５以下の整数である。ｔ９は０以上（ｔ８＋３）以下の整数である。Ｘ^０１０は有機基である。 X ⁰² and X ⁰³ have been described above, and X ⁰² and X ⁰³ are preferably groups represented by the following formula (C1a-i) or (C1a-ii).

In formulas (C1a-i) and (C1a-ii), X ⁰⁸ and X ⁰⁹ are each organic groups. t6 is an integer of 0 or more and 4 or less. When X ⁰⁸ and X ⁰⁹ are present at adjacent positions on the benzene ring, X ⁰⁸ and X ⁰⁹ may combine with each other to form a ring. t7 is an integer of 1 or more and 8 or less. t8 is an integer of 1 or more and 5 or less. t9 is an integer from 0 to (t8+3). X ⁰¹⁰ is an organic group.

Examples of organic groups for X ⁰⁸ and X ⁰⁹ in formula (C1a-i) are the same as for X ⁰² and X ⁰³ . X ⁰⁸ is preferably an alkyl group or a phenyl group. When X ⁰⁸ is an alkyl group, the number of carbon atoms thereof is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Thus, X ⁰⁸ is most preferably a methyl group. When X ⁰⁸ and X ⁰⁹ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by formula (C1a-i) in which X ⁰⁸ and X ⁰⁹ form a ring include naphthalen-1-yl group and 1,2,3,4 -tetrahydronaphthalen-5-yl group and the like. In the above formula (C1a-i), t6 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In formula (C1a-ii) above, X ⁰¹⁰ is an organic group. Examples of the organic group include groups similar to the organic groups described for X ⁰² and X ⁰³ . Among organic groups, alkyl groups are preferred. Alkyl groups may be straight or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. X ⁰¹⁰ is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.

In formula (C1a-ii) above, t8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (C1a-ii), t9 is 0 or more and (t8+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0. In formula (C1a-ii) above, t7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (C1a), X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. be. A phenyl group, a naphthyl group and the like are preferably exemplified as substituents which may be possessed when X ⁰⁴ and X ⁰⁵ are alkyl groups. In addition, when X ⁰⁴ and X ⁰⁵ are aryl groups, the substituents which may be present include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and the like. are preferably exemplified.

In formula (C1a), X ⁰⁴ and X ⁰⁵ are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like. Preferred examples are, among these, a methyl group or a phenyl group is more preferred.

As described above, X ⁰¹ is preferably a group represented by formula (C1a-1aa), a group represented by formula (C1a-1ba), and a group represented by formula (C1a-1ca).
Preferred specific examples of the oxime ester compound represented by formula (C1a) when X ⁰¹ is a group represented by formula (C1a-1aa) include the following compounds.

Preferred specific examples of the oxime ester compound represented by formula (C1a) when X ⁰¹ is a group represented by formula (C1a-1ba) include the following compounds.

Preferred specific examples of the oxime ester compound represented by formula (C1a) when X ⁰¹ is a group represented by formula (C1a-1ca) include the following compounds.

（式（Ｃ１ｂ）中、Ｒ^ｃ１はニトロ基であり、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ２とＲ^ｃ３とは相互に結合して環を形成してもよく、Ｒ^ｃ４は１価の有機基であり、Ｒ^ｃ５は、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｎ１は１以上４以下の整数であり、ｍ１は０又は１である。） (Oxime ester compound (C1b))
The oxime ester compound (C1b) is a compound represented by the following formula (C1b).

(In the formula (C1b), R ^c1 is a nitro group, R ^c2 and R ^c3 are each an optionally substituted linear alkyl group, an optionally substituted cyclic organic group, or a hydrogen atom, R ^c2 and R ^c3 may be bonded to each other to form a ring, R ^c4 is a monovalent organic group, R ^c5 is a hydrogen atom and may have a substituent an alkyl group having 1 or more and 11 or less carbon atoms, or an optionally substituted aryl group, n1 is an integer of 1 or more and 4 or less, and m1 is 0 or 1.)

In formula (C1b), R ^c1 is a nitro group. R ^c1 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by —(CO) _m1 — on the fluorene ring in formula (C1b). In formula (C1b), the bonding position of R ^c1 to the fluorene ring as long as it is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by —(CO) _m1 — on the fluorene ring. is not particularly limited. When the compound represented by the formula (C1b) has one or more R ^c1 , one of the one or more R ^c1 is a fluorene ring, because the compound represented by the formula (C1b) is easy to synthesize. It is preferred to bind to the 2nd position in the When there is more than one R ^c1 , the plurality of R ^c1s may be the same or different.

In formula (C1b), R ^c2 and R ^c3 are each an optionally substituted chain alkyl group, an optionally substituted cyclic organic group, or a hydrogen atom. R ^c2 and R ^c3 may combine with each other to form a ring. Among these groups, chain alkyl groups which may have a substituent are preferable as ^Rc2 and ^Rc3 . When R ^c2 and R ^c3 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c2 and R ^c3 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable. Specific examples of R ^c2 and R ^c3 being chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups. , n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group. In addition, when R ^c2 and R ^c3 are alkyl groups, the alkyl group may contain an ether bond (--O--) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.

When R ^c2 and R ^c3 are chain alkyl groups having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. . In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. A chain alkyl group having a substituent is preferably linear.
The substituents that the alkyl group may have are not particularly limited as long as they do not interfere with the object of the present invention. Suitable examples of substituents include cyano groups, halogen atoms, cyclic organic groups, alkoxycarbonyl groups, and the like.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, fluorine atom, chlorine atom, bromine atom and the like are preferable.
Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, heterocyclyl groups, and the like. The number of carbon atoms in the cycloalkyl group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups. A heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a fused group of such monocyclic rings or such monocyclic rings and a benzene ring. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. A heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
The number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert- butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy carbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. is mentioned.

When the chain alkyl group has substituents, the number of substituents is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^c2 and R ^c3 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups. When R ^c2 and R ^c3 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as in the case where R ^c2 and R ^c3 are chain alkyl groups.

When R ^c2 and R ^c3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is a phenyl group or a group formed by combining multiple benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.

When R ^c2 and R ^c3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. Although the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, A tetracyclododecyl group, an adamantyl group, and the like can be mentioned.

When R ^c2 and R ^c3 are heterocyclyl groups, the heterocyclyl groups are 5- or 6-membered monocyclic rings containing one or more of N, S, O, or such monocyclic rings together, or such monocyclic rings and a benzene ring. is a fused heterocyclyl group. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. A heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.

R ^c2 and R ^c3 may combine with each other to form a ring. A group consisting of a ring formed by R ^c2 and R ^c3 is preferably a cycloalkylidene group. When R ^c2 and R ^c3 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- or 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ^c2 and R ^c3 is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and pyridine. ring, pyrazine ring, pyrimidine ring, and the like.

Preferred specific examples of R ^c2 and R ^c3 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl groups; 2-methoxyethyl; group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n -pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and cyanoalkyl groups such as 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl groups. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy carbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n -Alkoxycarbonylalkyl groups such as heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n- pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n- butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Preferred groups among those described above for R ^c2 and R ^c3 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^c4 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy group, substituted A phenylalkyl group optionally having a group, a naphthyl group optionally having a substituent, a naphthoxy group optionally having a substituent, a naphthoyl group optionally having a substituent, a group optionally having a substituent optionally substituted naphthoxycarbonyl group, optionally substituted naphthyloxy group, optionally substituted naphthylalkyl group, optionally substituted heterocyclyl group, optionally substituted heterocyclylcarbonyl group, amino group substituted with one or two organic groups, morpholin-1-yl group, piperazin-1-yl group and the like.

When R ^c4 is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. Also, when R ^c4 is an alkyl group, it may be linear or branched. Specific examples of R ^c4 being an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl groups. , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group and the like. In addition, when R ^c4 is an alkyl group, the alkyl group may contain an ether bond (--O--) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.

When R ^c4 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R ^c4 is an alkoxy group, it may be linear or branched. Specific examples of R ^c4 being an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n -pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octioxyl group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. Further, when R ^c4 is an alkoxy group, the alkoxy group may contain an ether bond (--O--) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.

When R ^c4 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of R ^c4 being a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of R ^c4 being a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c4 is a saturated aliphatic acyl group or saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples of R ^c4 being a saturated aliphatic acyl group include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Noyl group, n-hexadecanoyl group and the like. Specific examples of R ^c4 being a saturated aliphatic acyloxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c4 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of R ^c4 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyl oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and An isodecyloxycarbonyl group and the like can be mentioned.

When R ^c4 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When R ^c4 is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of R ^c4 being a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group. Specific examples of R ^c4 being a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. be done. When R ^c4 is a phenylalkyl group or a naphthylalkyl group, R ^c4 may further have a substituent on the phenyl group or naphthyl group.

When R ^c4 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or such monocyclic rings are fused together or such monocyclic rings are fused with a benzene ring. is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. A heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done. When R ^c4 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c4 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^c4 is a heterocyclyl group.

When R ^c4 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted 7 to 20 carbon atoms The following phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthoyl groups, optionally substituted naphthylalkyl groups having 11 to 20 carbon atoms, and heterocyclyl and the like. Specific examples of these suitable organic groups are the same as the organic groups for R ^c4 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group and the like.

Substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, and alkyl groups having 1 to 6 carbon atoms , a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 further have substituents, the number of substituents is not limited as long as the object of the present invention is not impaired, but 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c4 have multiple substituents, the multiple substituents may be the same or different.

^Rc4 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ^c4 may have.

Among the organic groups, R ^c4 is an alkyl group, a cycloalkyl group, an optionally substituted phenyl group or a cycloalkylalkyl group, an optionally substituted phenylthio Alkyl groups are preferred. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, most preferably a methyl group. preferable. Among the optionally substituted phenyl groups, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferred.

（式（Ｒｃ４－１）及び（Ｒｃ４－２）中、Ｒ^ｃ１１及びＲ^ｃ１２はそれぞれ有機基であり、ｐは０以上４以下の整数であり、Ｒ^ｃ１１及びＲ^ｃ１２がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１１とＲ^ｃ１２とが互いに結合して環を形成してもよく、ｑは１以上８以下の整数であり、ｒは１以上５以下の整数であり、ｓは０以上（ｒ＋３）以下の整数であり、Ｒ^ｃ１３は有機基である。） R ^c4 has been described above, and R ^c4 is preferably a group represented by the following formula (Rc4-1) or (Rc4-2).

(In formulas (Rc4-1) and (Rc4-2), R ^c11 and R ^c12 are each an organic group, p is an integer of 0 or more and 4 or less, and R ^c11 and R ^c12 are adjacent on a benzene ring. position, R ^c11 and R ^c12 may combine with each other to form a ring, q is an integer of 1 or more and 8 or less, r is an integer of 1 or more and 5 or less, and s is 0 is an integer not less than (r+3) and not more than (r+3), and R ^c13 is an organic group.)

Examples of organic groups for R ^c11 and R ^c12 in formula (Rc4-1) are the same as for R ^c4 . R ^c11 is preferably an alkyl group or a phenyl group. When R ^c11 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^c11 is most preferably a methyl group. When R ^c11 and R ^c12 combine to form a ring, the ring may be either an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (Rc4-1) in which R ^c11 and R ^c12 form a ring include naphthalen-1-yl, 1,2,3, 4-tetrahydronaphthalen-5-yl group and the like. In the above formula (Rc4-1), p is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In the above formula (Rc4-2), ^Rc13 is an organic group. Examples of the organic group include groups similar to the organic groups described for R ^c4 . Among organic groups, alkyl groups are preferred. Alkyl groups may be straight or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. R ^c13 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.

In the above formula (Rc4-2), r is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (Rc4-2), s is 0 or more and (r+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0. In the above formula (Rc4-2), q is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (C1b), R ^c5 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. A phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed when R ^c5 is an alkyl group. In addition, when R ^c5 is an aryl group, the substituent that may be possessed includes preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like.

In formula (C1b), R ^c5 is preferably exemplified by a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, and the like. , among these, a methyl group or a phenyl group is more preferable.

Specific examples of the compound represented by formula (C1b) include the following compounds.

[Compound (C2)]
The compound (C2) is at least one selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b).

式（Ｃ２ａ－１）中、Ｒ^ｃ２１及びＲ^ｃ２２は、それぞれ独立に、アルキル基、シクロアルキル基、アリール基、炭素原子数２以上２０以下の脂肪族アシル基、又は炭素原子数７以上２０以下の芳香族アシル基である。ただし、Ｒ^ｃ２１及びＲ^ｃ２２の双方が脂肪族アシル基又は芳香族アシル基ではない。 (Phosphine oxide compound (C2a))
A phosphine oxide compound (C2a) is a pentavalent phosphorus compound having a P=O bond.
Examples of the phosphine oxide compound (C2a) include compounds having a partial structure represented by the following formula (C2a-1).

In formula (C2a-1), R ^c21 and R ^c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or 7 to 20 carbon atoms. is an aromatic acyl group of However, both R ^c21 and R ^c22 are not aliphatic acyl groups or aromatic acyl groups.

The number of carbon atoms in the alkyl groups of R ^c21 and R ^c22 is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less. The alkyl groups as R ^c21 and R ^c22 may be linear or branched.
Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert- pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group and the like.

The number of carbon atoms in the cycloalkyl groups for R ^c21 and R ^c22 is preferably 5 or more and 12 or less. Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups.

The number of carbon atoms in the aryl groups of R ^c21 and R ^c22 is preferably 6 or more and 12 or less. The aryl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and the like. Specific examples of aryl groups include phenyl and naphthyl groups.

The number of carbon atoms in the aliphatic acyl groups for R ^c21 and R ^c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less. Aliphatic acyl groups may be straight or branched.
Specific examples of aliphatic acyl groups include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, and tetradecanoyl groups. , pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, and icosanoyl group.

The number of carbon atoms in the aromatic acyl groups for R ^c21 and R ^c22 is 7 or more and 20 or less. The aromatic acyl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and the like. Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6- trimethylbenzoyl group, α-naphthoyl group, β-naphthoyl group and the like.

Preferable specific examples of the phosphine oxide compound containing the structural moiety represented by formula (C2a-1) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl). -phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

(Aminoketone compound (C2b))
The aminoketone-based compound (C2b) is a ketone compound having an amino group that can be used as a photopolymerization initiator. The aminoketone-based compound (C2b) is typically an α-aminoketone-based compound, which is a carbonyl compound to which an amino group optionally substituted at the α-position is bonded.
Examples of aminoketone compounds (C2b) include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butan-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-morpholino Phenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one, 2 α-aminoketone compounds such as -ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

The photosensitive composition preferably contains a combination of a phosphine oxide compound (C2a) and an aminoketone compound (C2b) as the compound (C2), since a cured film having excellent water resistance can be easily formed. The mass ratio of compound (C2a) and compound (C2b) when they are combined is preferably 60:40 to 40:60. Further, when the photopolymerization initiator (C) includes an oxime ester compound (C1), a phosphine oxide compound (C2a) and an aminoketone compound (C2b) in combination, the compound (C1), the compound (C2a) and The mass ratio to the total amount of the compound (C2b) is preferably from 90:10 to 50:50, more preferably from 85:15 to 75:25 in terms of forming a good taper angle pattern.

The photopolymerization initiator (C) may contain a photopolymerizable compound other than the oxime ester compound (C1) and the compound (C2). The total content of the oxime ester compound (C1) and the compound (C2) in the photopolymerization initiator (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.

The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less with respect to the total mass of the solid content of the photosensitive composition. It is preferably 1% by mass or more and 10% by mass or less, more preferably.

<Light shielding agent (D)>
The photosensitive composition contains a light shielding agent (D). By including the light-shielding agent (D) in the photosensitive composition, the photosensitive composition is preferably used, for example, for forming black matrices and black column spacers in color filters of display devices.
The light-shielding agent (D) contains titanium nitride and/or titanium oxynitride (hereinafter each or collectively referred to herein as metal nitride).
By using the light-shielding agent (D) containing titanium nitride and/or titanium oxynitride, it is possible to form a cured film with low transmittance for light with a wavelength of 800 to 1000 nm using a photosensitive composition.
The light-shielding agent (D) contains other coloring agents other than titanium nitride and/or titanium oxynitride within a range in which the light-shielding property of the cured film formed using the photosensitive composition is not significantly impaired. good too. Other colorants may be pigments or dyes. The hue of other colorants is not limited to black. The hue of other colorants may be chromatic. In the present invention, the components of the light shielding agent (D) excluding the dispersant are preferably titanium nitride and/or metal nitrides of titanium oxynitride.

The average primary particle size of the light shielding agent (D) containing titanium nitride and/or titanium oxynitride is preferably 10 nm or more and 45 nm or less.
The average primary particle size can be measured based on a transmission electron microscope image (TEM image) of the light shielding agent (D).
First, the maximum diameter Dmax of primary particles in the TEM image is measured. The maximum diameter is the maximum distance between any two points on the contour of the primary particle in the TEM image.
The maximum vertical length DV-max is defined by arranging two straight lines parallel to the straight line giving Dmax out of the straight lines connecting any two points on the contour of the primary particles in the TEM image so as to sandwich the primary particles. It is the distance between two parallel straight lines when circumscribing the outline of a primary particle.
The geometric mean diameter of the maximum diameter Dmax and the maximum vertical length DV-max is defined as the particle diameter of the primary particles. The geometric mean diameter is calculated by the following formula.
Geometric mean diameter = (Dmax x DV-max) ^0.5
Let the arithmetic average value of the particle diameter of arbitrary 100 primary particles be the average primary particle diameter of a light shielding agent (D).

The amount of the light-shielding agent (D) used in the photosensitive composition can be appropriately selected within a range that does not hinder the object of the present invention. Typically, the amount of the light-shielding agent (D) used is preferably 2% by mass or more and 75% by mass or less, more preferably 3% by mass or more and 70% by mass or less, relative to the total mass of the solid content of the photosensitive composition. preferable.

In particular, when a photosensitive composition is used to form a cured film as a light-shielding screen for an image display device such as a black matrix, the photosensitive composition should be such that the OD value per 1 μm of the cured film is 1 or more. It is preferred to adjust the amount of sunscreen in the composition.

The light-shielding agent (D) is preferably dispersed in the presence or absence of a dispersing agent at an appropriate concentration to form a dispersion, and then added to the photosensitive composition.
In this specification, the amount of the light-shielding agent (D) used can be defined as a value including this dispersant present.

<Solvent (S)>
Examples of the solvent (S) contained in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, Propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono (Poly)alkylene glycol monoalkyl ethers such as ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; - Lactic acid alkyl esters such as methyl hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate and methyl 3-ethoxypropionate , ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, pyruvic acid other esters such as methyl, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, and amides such as N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are the above-mentioned (A ) and (B) components, and can improve the dispersibility of the above-mentioned component (C). Propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferably used. is particularly preferred.

The content of the solvent (S) is preferably an amount such that the solid content concentration of the photosensitive composition is 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and 10% by mass. A more preferable amount is 30% by mass or less.

<Other ingredients>
The photosensitive composition may contain various additives as necessary. Various additives include sensitizers, curing accelerators, photocrosslinkers, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, UV absorbers, aggregation inhibitors, and thermal polymerization inhibitors. agents, antifoaming agents, surfactants, silane coupling agents and the like.

Examples of thermal polymerization inhibitors include hydroquinone and hydroquinone monoethyl ether. Examples of antifoaming agents include silicone-based and fluorine-based compounds, and surfactants include anionic, cationic, and nonionic compounds.

<Method for preparing photosensitive composition>
The above photosensitive composition can be prepared by stirring, mixing, dissolving or dispersing the above components. Mixing may be performed using a stirrer such as a roll mill, ball mill, or sand mill. It can be prepared by filtering with a filter such as a 2 μm membrane filter, if necessary.

<<Method for producing patterned cured film>>
By curing the photosensitive composition described above by exposure, a colored film can be obtained as a cured product.
In particular, because it is possible to form a fine cured film that is difficult to peel off from the substrate,
The cured film produced using the photosensitive composition described above has excellent adhesion to the substrate and can have a tapered cross section with an appropriate taper angle. It can be preferably used in applications requiring adhesion to a substrate and a tapered cross section having an appropriate taper angle.
Thus, the aforementioned photosensitive composition is suitably used for forming a patterned cured film.
A patterned cured film is typically
Forming a coating film by coating the photosensitive composition on a substrate;
position-selectively exposing the coating film;
Developing the exposed coating film;
manufactured by a method comprising:

Each step will be described below. Forming a coating film by applying a photosensitive composition is referred to as a “coating film forming step”. Position-selectively exposing the coating film is referred to as an “exposure step”. Developing the coating film after exposure is referred to as a “development step”.

<Coating film forming process>
In the coating film forming step, a coating film is formed by coating the photosensitive composition on the substrate.
The type of substrate is not particularly limited, and various substrates used in optical devices such as liquid crystal display devices, organic EL display devices, and organic TFT arrays can be used as appropriate. Examples of substrates include quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, SOG (Spin On Glass), polyester films, polycarbonate films, and polyimides. Polymer substrates such as films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc. and the like. Furthermore, in the case of forming a laminated structure on a substrate, for example, any layer which is already formed on the substrate and which is to be a substructure is also included in the concept of the substrate to which the photosensitive composition is applied. Also, the shape of the substrate is not particularly limited, and may be plate-like or roll-like. The base material may have unevenness on the surface, for example, according to various patterns. Moreover, as the base material, a light-transmitting or non-light-transmitting base material can be selected.

In the coating film forming step, for example, a contact transfer coating device such as a roll coater, a reverse coater, and a bar coater, or a non-contact coating device such as a spinner (rotary coating device) or a curtain flow coater is used to form a photosensitive layer on the substrate. A composition is applied, and if necessary, the solvent is removed by drying (pre-baking) to form a coating film.

The film thickness of the coating film is not particularly limited. The thickness of the coating film is preferably 0.05 μm or more, more preferably 1 μm or more. The thickness of the coating film may be, for example, 7 μm or more, or may be 10 μm or more. Although there is no particular upper limit for the thickness of the coating film, it may be, for example, 50 μm or less, or 20 μm or less. The thickness of the coating film is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less.

The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at a temperature of 80° C. to 120° C., preferably 90° C. to 100° C. for 60 seconds to 120 seconds, ( 2) a method of leaving the sample at room temperature for several hours to several days;

<Exposure process>
In the exposure step, the coating film formed in the coating film forming step is position-selectively exposed. A patterned cured film is obtained by position-selectively exposing and developing according to a desired pattern shape.

In the exposure step, exposure is performed by irradiation with active energy rays such as ultraviolet rays and excimer laser light. When forming a patterned cured film, the coating film is selectively exposed to light through, for example, a negative mask. Although the exposure amount varies depending on the composition of the photosensitive composition, it is preferably 10 mJ/cm ² or more and 100 mJ/cm ² or less. Perhaps because the above-described photosensitive composition has excellent sensitivity, it exhibits excellent adhesion to the substrate even at a low exposure dose of, for example, 10 mJ/cm ² or more and 30 mJ/cm ² or less, or even 10 mJ/cm ² or more and 20 mJ/cm ² or less. A hardened film can be formed, and a pattern having a moderately tapered cross section can be formed.

A cured film cured by exposure may be heated. The temperature for heating is not particularly limited, and is preferably 180° C. or higher and 280° C. or lower, more preferably 200° C. or higher and 260° C. or lower, and particularly preferably 220° C. or higher and 250° C. or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

<Development process>
In the development process, the coating film exposed in the exposure process is developed with a developer such as an alkaline developer.
In the development step, the exposed coating film is developed with a developer to form a cured product patterned into a desired shape. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. A developer is appropriately selected according to the composition of the photosensitive composition. As the developer, an organic developer such as monoethanolamine, diethanolamine, or triethanolamine, or an aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, or a quaternary ammonium salt can be used.

After development, post-baking may be performed as necessary. The post-development post-baking temperature is preferably 80° C. or higher and 250° C. or lower, more preferably 100° C. or higher and 230° C. or lower. The post-development post-baking time is preferably 5 minutes or more and 60 minutes or less, more preferably 10 minutes or more and 30 minutes or less.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited to these Examples.

[Preparation of Resin A1]
Into a 500 mL four-necked flask, 235 g of a bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were charged. was heated to 90° C. or higher and 100° C. or lower while blowing air into it at a rate of 25 mL/min to dissolve it. Next, the solution was gradually heated to 120° C. while the solution was still cloudy and dissolved completely. At this time, the solution gradually became transparent and viscous, but the stirring was continued. During this time, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula.

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, followed by 3,3′,4,4′-biphenyltetracarboxylic dianhydride. 79.4 g and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised and reacted at 110° C. or higher and 115° C. or lower for 4 hours. After confirming the disappearance of the acid anhydride groups, 41.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain Resin A1. Resin A1 is a compound represented by formula (a-1). Disappearance of acid anhydride groups was confirmed by IR spectrum.
The mass average molecular weight of Resin A1 was 4,500.

[Examples 1 to 15 and Comparative Examples 1 to 5]
<Alkali-soluble resin (A) (component A)>
As the alkali-soluble resin (A), the above resin A1 and the following resin 2 were used. Resin 2 is a copolymer composed of 45% by mass of methacrylic acid-derived structural units and 55% by mass of benzyl methacrylate, and 1/3 of the methacrylic acid-derived structural units is 3,4-epoxycyclohexyl. It is an acrylic resin having unsaturated double bonds reacted with methyl methacrylate.

<Photopolymerizable monomer (B) (B component)>
B1, B2, and B3 below were used as the photopolymerizable monomer (B).
B1: Dipentaerythritol hexaacrylate B2: Glycerin triacrylate B3: Glycerin-1,3-diacrylate

<Photoinitiator (C) (component C)>
As the oxime ester compound (C1) (C1 component), the following C1-a, C1-b, and C1-c were used.

The following C2-a and C2-b were used as compound (2).

<Light shielding agent (D) (component D)>
D1 and D2 below were used as the light shielding agent (D) (component (D)).
The amount of the light shielding agent (D) described in Table 1 below is not the amount of the dispersion, but the solid content (the amount of the light shielding agent and the dispersing agent) in the dispersion.
D1: Metal nitride dispersion containing titanium nitride and titanium oxynitride (metal nitride content 30% by mass, metal nitride average particle size: 30 nm, urethane dispersant content 10% by mass, dispersion medium: 3- methoxybutyl acetate (MA))
D2: Carbon black dispersion (carbon black content 20% by mass, urethane dispersant content 15% by mass, dispersion medium: 3-methoxybutyl acetate (MA))

28.8 parts by mass of the alkali-soluble resin (A) of the type shown in Table 1, 4 parts by mass of each of the two photopolymerizable monomers (B) of the type shown in Table 1, and the types and amount of photopolymerization initiator (C), 60.0 parts by mass of light-shielding agent (D) of the type described in Table 1, 0.1 part by mass of surfactant (BYK310, manufactured by BYK-Chemie), and 0.1 part by mass. 1 part by mass of a silane coupling agent (3-(phenylamino)propyltrimethoxysilane), 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PM) so that the solid content concentration is 25 mass ) in a mixed solvent (MA/PM=60/40 (mass ratio)) to obtain a photosensitive composition of each example and comparative example.
Only in Example 11, 0.2 parts by mass of surfactant was used and no silane coupling agent was used.

[Evaluation of OD value]
After applying the photosensitive composition onto a 6-inch glass substrate (1737 glass manufactured by Dow Corning), the composition was dried at 90° C. for 60 seconds to form a coating film. Next, this coated film was irradiated with ghi rays at an exposure amount of 60 mJ/cm ² . Then, post-baking was performed on a hot plate at 230° C. for 20 minutes. The film thickness of the cured film formed was three levels of 0.8 μm, 1.0 μm and 1.2 μm. For this cured film, the OD value at each film thickness was measured using D200-II (manufactured by Macbeth), and the OD value per 1 μm was calculated from an approximate curve.
When the OD value was measured by the above method, the OD value was 3.0/μm in any of the examples and comparative examples.

[Evaluation of water resistance]
After coating the photosensitive composition on a glass substrate (Eagle XG manufactured by Dow Corning), it was dried at 100° C. for 120 seconds to form a coating film. Next, this coating film was irradiated with ghi rays at an exposure amount of 100 mJ/cm ² . Then, post-baking was performed on a hot plate at 230° C. for 30 minutes. The film thickness of the formed cured film was 1.2 μm. The resulting cured film was cross-cut according to ASTM D3359-09e2. The substrate provided with the cross-cut cured film was held in a water atmosphere of 120° C. and 2 atm (G) for 24 hours in a pressure vessel. After drying the substrate with the cured film taken out of the pressure container, a test for observing peeling of the cured film by sticking and peeling the adhesive tape to the cross-cut cured film was performed according to ASTM D3359-09e2. . Based on the observed peeling state of the cured film, the water resistance of the cured film was evaluated according to the following criteria. Table 1 shows the evaluation results of water resistance.
⊚: After the adhesive tape was peeled off, the peeled cured film did not adhere to the adhesive tape.
◯: After peeling off the adhesive tape, the number of squares of the cured film adhering to the adhesive tape was less than 5% of the total number of squares.
x: After peeling off the adhesive tape, the number of squares of the cured film adhering to the adhesive tape was 5% or more of the total number of squares.

[Pattern evaluation]
The photosensitive compositions of Examples and Comparative Examples were applied onto a glass substrate (100 mm×100 mm) using a spin coater and prebaked at 70° C. for 120 seconds to form coating films. Then, using a proximity exposure apparatus (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap is set to 50 μm, and through a negative mask having a line and space pattern with a line width of 6 μm and a space width of 6 μm. , the coating film was irradiated with ultraviolet rays. The exposure dose was 150 mJ/cm ² . After the exposure, the coating film was developed with a 0.04 mass % KOH aqueous solution at 26° C. for 50 seconds, and then post-baked at 230° C. for 30 minutes to form a line-and-space pattern with a film thickness of 3.5 μm.

(Pattern straightness evaluation)
The formed line pattern was observed with an optical microscope to evaluate the straightness of the pattern. The straightness of the pattern was evaluated as "good" when there was no rattling at the edge of the line, and as "bad" when there was rattling.

(Pattern peeling evaluation)
The formed line-and-space pattern was observed with an optical microscope to confirm the presence or absence of pattern peeling, and evaluated according to the following criteria. Table 1 shows the results.
◎: No pattern peeling ○: Peeling was observed in 2 or less lines per 10 lines ×: Peeling was observed in 3 or more lines per 10 lines

(Tapered shape)
A taper angle was evaluated for a line-and-space pattern formed with an exposure dose of 20 mJ/cm ² . The taper angle was measured as the bonding angle between the pattern and the substrate with a scanning electron microscope. This taper angle corresponds to the angle θ in FIGS. 1(a) and 1(b). The tapered shape measured according to the following criteria was evaluated. Table 1 shows the results.
◎: 70 ° or more and 85 ° or less ○: 85 ° or more and less than 90 ° △: 90 ° or more and less than 100 ° ×: more than 100 °

According to Table 1, it contains an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and titanium nitride and/or titanium oxynitride as a light shielding agent (D). and the photopolymerization initiator (C) comprises an oxime ester compound (C1) and at least one compound (C2) selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b) in combination. The photosensitive compositions of Examples containing the photopolymerization initiator (C) cured well, had excellent water resistance, and provided a patterned cured film having a tapered cross section with an appropriate taper angle. I understand.
On the other hand, when using the photosensitive composition of the comparative example that does not contain the compound (C2) as the photopolymerization initiator (C) or does not contain titanium nitride and/or titanium oxynitride as the light shielding agent (D), water resistance It has been difficult to form a patterned cured film having a tapered cross-section with an excellent taper angle and a moderate taper angle.

1 Cross-section in the width direction of a pattern with no undercut 2 Cross-section in the width direction of a pattern with an undercut

Claims (8)

A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D), wherein the photopolymerization initiator (C) is an oxime ester compound (C1) in combination with at least one compound (C2) selected from phosphine oxide compounds (C2a) and aminoketone compounds (C2b),
The photosensitive composition, wherein the light shielding agent (D) contains titanium nitride and/or titanium oxynitride. The photosensitive composition according to claim 1, wherein the photopolymerization initiator (C) comprises an oxime ester compound (C1), a phosphine oxide compound (C2a), and an aminoketone compound (C2b) in combination. . Claim 1 or 2, wherein the oxime ester compound (C1) exhibits a gram extinction coefficient of 2.0 mL/g cm or more at a measurement wavelength of 405 nm when measured as a solution of propylene glycol monomethyl ether. The photosensitive composition according to . Claims 1 to 3, wherein the ratio of the mass of said compound (C2) to the total mass of said oxime ester compound (C1) and said compound (C2) is 10% by mass or more and 40% by mass or less. The photosensitive composition according to any one of . The oxime ester compound (C1) has the following formula (C1a):

(In formula (C1), X ⁰¹ is the following formula (C1-1):

In the structure represented by, of the hydrogen atoms bonded to the aromatic ring, a group excluding t2 + t3 hydrogen atoms, X ⁰² and X ⁰³ are each independently a monovalent organic group, and X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, and t0 to t3 are each independently 0 or 1, at least one of t2 and t3 is 1;
In formula (C1-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring via a C—N bond, t4 and t5 are each independently 0 or 1, and t4 and At least one of t5 is 1. )
The photosensitive composition according to any one of claims 1 to 4, comprising a compound represented by The oxime ester compound (C1) has the following formula (C1b):

(R ^c1 is a nitro group, R ^c2 and R ^c3 are each an optionally substituted linear alkyl group, an optionally substituted cyclic organic group, or a hydrogen atom, and R ^c2 and R ^c3 may be bonded to each other to form a ring, R ^c4 is a monovalent organic group, R ^c5 is a hydrogen atom, or has 1 or more carbon atoms which may have a substituent. an alkyl group of 11 or less, or an aryl group which may have a substituent, n1 is an integer of 1 or more and 4 or less, and m1 is 0 or 1.)
The photosensitive composition according to any one of claims 1 to 4, comprising a compound represented by Forming a coating film by applying the photosensitive composition according to any one of claims 1 to 6 on a substrate;
position-selectively exposing the coating film;
developing the exposed coating film;
A method for producing a patterned cured film, comprising: A patterned cured film comprising a cured product of the photosensitive composition according to any one of claims 1 to 6.

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