TW201937286A - Photosensitive composition, cured product, cured product forming method, color filter and image display device capable of presenting excellent light-shielding properties and insulating properties - Google Patents

Abstract

The object of the present invention is to provide a photosensitive composition that has excellent light-shielding properties and insulating properties and is capable of forming a cured film having a desired cross-sectional shape, and also provide a cured product of the photosensitive composition, a color filter including a black matrix made of the cured product, an image display panel including the color filter, an image display device including the image display panel, and a method of using the photosensitive composition to produce a patterned cured film. In the photosensitive composition containing a light shielding agent in accordance with the present invention, an oxime ester compound having a specific structure is used as a photopolymerization initiator, and resin-coated carbon black is used as the light shielding agent.

Description

Photosensitive composition, cured product, cured product forming method, color filter, and image display device

The present invention relates to a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product formed using the photosensitive composition, a color filter including the cured product, and a video display device.

In a panel for a display device such as a liquid crystal display device, a patterned light-shielding film such as a black matrix or a black pillar spacer is usually formed. In such use, various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator for forming a light-shielding film are proposed.

For example, as a material for forming a black matrix, a negative photosensitive resin composition containing a photopolymerizable compound, a photopolymerization initiator, an acrylic resin fine particle dispersion in which acrylic resin fine particles are dispersed, carbon black, and a solvent is proposed ( Refer to Patent Document 1).
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-170075

[The problem that the invention wants to solve]

However, in the panel for image display devices, the image quality is increasingly sought. Therefore, in terms of improvement in contrast, etc., the black matrix is required to further improve the light blocking property. For example, when a black matrix is formed using the photosensitive resin composition described in Patent Document 1, the light-shielding property of the formed black matrix can be improved by increasing the content of carbon black in the photosensitive resin composition.
However, when the content of the carbon black in the photosensitive resin composition is increased, the insulating property (resistance value) of the formed black matrix is lowered or the sensitivity of the photosensitive resin composition is lowered, which is difficult to form. The case of a black matrix of the desired cross-sectional shape.

The present invention has been made in view of the above-described problems, and an object of the invention is to provide a photosensitive composition which can form a cured film having a desired light-shielding property and insulating property and has a desired cross-sectional shape, and a cured product of the photosensitive composition, A color filter of a black matrix of a cured product, an image display panel including the color filter, an image display device including the image display panel, and a method of manufacturing a patterned cured film using the photosensitive composition.
[Technical means to solve the problem]

The inventors of the present invention have conducted intensive studies, and as a result, it has been found that by using a phthalate compound having a specific structure as a photopolymerization initiator in a photosensitive composition containing an opacifier, and using a resin-coated carbon black as an opacifier, the above solution can be solved. The subject matter is thus completed.

The first aspect of the present invention is a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and an opacifier (D), and The photopolymerization initiator (C) contains the oxime ester compound (C1) represented by the following formula (c1):
[Chemical 1]

(In the formula (c1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, R ³ is a monovalent organic group, and R ⁴ is a monovalent organic group. R ⁵ and R ⁶ are each independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and m1, m2 and m3 are each 0 or 1),
The oxime ester compound (C1) satisfies at least one of the following conditions (1) to (3):
(1) R ¹ contains a group represented by -OR ⁷ and R ⁷ is a haloalkyl group
(2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent,
The sunscreen (D) contains a resin-coated carbon black (D1).

The second aspect of the present invention is a cured product of the photosensitive composition of the first aspect.

According to a third aspect of the present invention, there is provided a color filter comprising a black matrix of a cured product of the photosensitive composition of the second aspect.

A fourth aspect of the present invention is an image display panel including a color filter of a third aspect.

A fifth aspect of the present invention is the image display device of the image display panel of the fourth aspect.

A sixth aspect of the present invention is a method of producing a patterned cured film, comprising:
Applying the photosensitive composition of the first aspect to the substrate to form a coating film,
Selectively exposing the coating film,
The exposed coating film is developed.
[Effects of the Invention]

According to the present invention, it is possible to provide a photosensitive composition capable of forming a cured film having excellent light-shielding properties and insulating properties and having a desired cross-sectional shape, a cured product of the photosensitive composition, and a color filter having a black matrix containing the cured product. A light sheet, an image display panel including the color filter, an image display device including the image display panel, and a method of manufacturing a patterned cured film using the photosensitive composition.

≪Photosensitive composition≫
The photosensitive composition contains an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and an opacifier (D). The photopolymerization initiator (C) contains an oxime ester compound (C1) having the specific structure described below. The sunscreen (D) contains a resin-coated carbon black (D1). The photosensitive composition may contain components such as an additive (E) and an organic solvent (S) as needed.

The film thickness of the cured film formed using the photosensitive composition is not particularly limited. The film thickness of the cured film is preferably 0.2 μm or more, more preferably 0.3 μm or more and 5 μm or less, further preferably 0.4 μm or more and 3 μm or less, and particularly preferably 0.5 μm or more and 2 μm or less.
In the following, an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), an opacifier (D), and an optional component, which are essential components contained in the photosensitive composition, A method for producing a cured product of a photosensitive composition will be described.

<alkali soluble resin (A)>
The photosensitive composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) is not particularly limited, and can be appropriately selected from alkali-soluble resins previously formulated in various photosensitive resin compositions.
In the present specification, the alkali-soluble resin (A) is a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, or the like) having an alkali solubility in a molecule.

The resin which is preferable as the alkali-soluble resin (A) is 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, a photosensitive composition excellent in resolution can be easily obtained, and a photosensitive composition can be easily used to form a cured film which is less likely to excessively flow by heating. Therefore, it is easy to form a cured film having a good cross-sectional shape.

[Resin with a Cardo structure (a-1)]
As the resin (a-1) having a Cardo skeleton, it can be used for a resin having a Cardo skeleton in its structure and having a specific alkali solubility. The Cardo skeleton refers to a skeleton in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. Further, the second annular structure and the third annular structure may have the same structure or different structures.
A typical example of the Cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to a carbon atom at the 9-position of the anthracene ring.

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

[Chemical 2]

In the formula (a-1), X ^a represents ^{a group} represented by the following formula (a-2). T1 represents an integer of 0 or more and 20 or less.

[Chemical 3]

In the above formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group, and R ^a3 independently represents a linear chain. Or a branched alkyl group, t2 represents 0 or 1, and W ^a represents ^{a group} represented by the following formula (a-3).

[Chemical 4]

In the formula (a-2), R ^{a3 is} preferably an alkylene group having 1 or more and 20 or less carbon atoms, more preferably an alkylene group having 1 or more and 10 or less carbon atoms, and particularly preferably a carbon atom number. The alkylene group of 1 or more and 6 or less is preferably an ethane-1,2-diyl group, a propane-1,2-diyl group and a propane-1,3-diyl group.

The ring A in the formula (a-3) represents an aliphatic ring which is condensable with an aromatic ring and which may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
The aliphatic ring may, for example, be a monocycloalkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane.
Specific examples thereof include a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane.
The aromatic ring condensable with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferred.

Preferred examples of the divalent group represented by the formula (a-3) include the following groups.
[Chemical 5]

Of formula (a-1) in the divalent group X ^a system by providing that the Z ^a residue of tetracarboxylic dianhydride of the following formula (a-2a) represented by reacting the diol compound Cardo introduced into the resin (a -1) Medium.
[Chemical 6]

In the formula (a-2a), R ^a1 , R ^a2 , R ^a3 and t2 are as described for the formula (a-2). Regarding the ring A in the formula (a-2a), it is as described with respect to the formula (a-3).

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.
First, if the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is substituted with a group represented by -R ^a3 -OH according to the usual method, epichlorohydrin is used. The glycidylation is carried out to obtain an epoxy compound represented by the following formula (a-2c).
Then, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid, whereby the diol compound represented by the formula (a-2a) is obtained.
In the formula (a-2b) and the formula (a-2c), R ^a1 , R ^a3 and t2 are as described for the formula (a-2). The ring A in the formula (a-2b) and the formula (a-2c) is as described for the formula (a-3).
Further, the method for producing the diol compound represented by the formula (a-2a) is not limited to the above method.
[Chemistry 7]

Preferred examples of the diol compound represented by the formula (a-2b) include the following diol compounds.
[化8]

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

Further, in the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyl tetracarboxylic acid represented by the following formula (a-4). Acid dianhydride, diphenyl ether tetracarboxylic dianhydride, and the like.
Further, in the above formula (a-1), t1 represents an integer of 0 or more and 20 or less.

[Chemistry 9]

(In the formula (a-4), R ^a4 , R ^a5 and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, and a fluorine atom, and t3 represents 0. Above and an integer below 12)

The alkyl group of R ^a4 in the formula (a-4) may be an alkyl group having 1 or more and 10 or less carbon atoms. By setting the number of carbon atoms of the alkyl group to be in this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, it is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and more preferably 1 or more and 6 or less, as the number of carbon atoms, which is easy to obtain a heat resistance. It is preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less.
In the case where R ^a4 is an alkyl group, the alkyl group may be linear or branched.

In the case of the Cardo resin which is excellent in heat resistance, R ^a4 in the formula (a-4) is more preferably independently a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. R ^a4 in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
In terms of ease of preparation of the high-purity tetracarboxylic dianhydride, the plurality of R ^a4 in the formula (a-4) are preferably the same group.

In the formula (a-4), t3 represents an integer of 0 or more and 12 or less. By setting the value of t3 to 12 or less, the purification of tetracarboxylic dianhydride can be facilitated.
The upper limit of t3 is preferably 5, more preferably 3, in terms of ease of purification of tetracarboxylic dianhydride.
The lower limit of t3 is preferably 1, more preferably 2, in terms of chemical stability of the tetracarboxylic dianhydride.
The t3 in the formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 or more and 10 or less carbon atoms of R ^a5 and R ^{a6 in} the formula (a-4) may be selected from the same group as the alkyl group having 1 or more and 10 or less carbon atoms which may be selected as R ^a4 .
In terms of purification of the tetracarboxylic dianhydride, R ^a5 and R ^{a6 are} preferably a hydrogen atom or a carbon number of 1 or more and 10 or less (preferably 1 or more and 6 or less, more preferably 1 or more). Further, it is preferably 5 or less, more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less alkyl groups, and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5. '',6,6''-tetracarboxylic dianhydride (alias "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''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6 ,6''-tetracarboxylic dianhydride (alias "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 , decane-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 -cyclohexanone-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-cycloundecyl-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid Anhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, hydrazine Alkan-2-non-α-cyclotridecyl-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-(methyl ring Pentanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexane Ketone)-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 or more and 40,000 or less, more preferably 1,500 or more and 30,000 or less, and still more preferably 2,000 or more and 10,000 or less. By setting it as the said range, good developability is acquired, and sufficient heat resistance and mechanical strength are acquired with respect to a hardened film.

[Novolak resin (a-2)]
The alkali-soluble resin (A) containing a novolak resin (a-2) is also preferable from the viewpoint of suppressing excessive heat flow of the cured film due to heating at the time of post-baking.
As the novolac resin (a-2), various novolac resins previously formulated in the photosensitive resin composition can be used. The novolak resin (a-2) is preferably a resin obtained by addition-condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenol") and an aldehyde under an acid catalyst. .

(phenols)
Examples of the phenol used in the production of the novolac resin (a-2) include phenol; cresols such as o-cresol, m-cresol, and p-cresol; and 2,3-xylenol and 2,4. - xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc.; o-ethylphenol, m-ethyl Ethylphenols such as phenol and p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and Alkylphenols such as tributylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, p-benzene Polyphenols such as diphenols, hydroquinone monomethyl ether, pyrogallol and phloroglucinol; alkyl polyphenols such as alkyl resorcinol, alkyl catechol and alkyl hydroquinone (any alkyl group has 1 or more and 4 or less carbon atoms); α-naphthol; β-naphthol; hydroxybiphenyl; and bisphenol A. These phenols may be used singly or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferred, and m-cresol and p-cresol are more preferably used in combination. In this case, by adjusting the blending ratio of the two, it is possible to adjust characteristics such as heat resistance of the black matrix formed using the photosensitive composition.
The blending ratio of m-cresol to p-cresol is not particularly limited, and is preferably 3/7 or more and 8/2 or less in terms of the molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in this range ratio, it is easy to obtain a photosensitive composition which can form a black matrix excellent in heat resistance.

Further, a novolak resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. In the case of using the novolak resin, it is particularly easy to obtain a photosensitive composition which can form a black matrix which is not easily excessively flowed by heating at the time of post-baking.
The blending ratio of m-cresol to 2,3,5-trimethylphenol is not particularly limited, and it is preferably 70/30 or more and 95% by mol ratio of m-cresol/2,3,5-trimethylphenol. /5 or less.

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

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

(molecular weight)
The polystyrene-equivalent weight average molecular weight (Mw; hereinafter also referred to as "weight average molecular weight") of the novolac resin (a-2), the black matrix formed by using the photosensitive composition, and the flow caused by heating From the viewpoint of patience, the lower limit is preferably 2,000, more preferably 5,000, still more preferably 10,000, still more preferably 15,000, most preferably 20,000, and the upper limit is preferably 50,000, more preferably 45,000. Further preferably, it is 40,000, and most preferably 35,000.

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

[Modified Epoxy Resin (a-3)]
As the alkali-soluble resin (A), it is possible to achieve higher flow resistance at the time of baking, and it is easy to impart a high water resistance to the cured film, and may contain an epoxy compound (a-3a) and not A polybasic acid anhydride (a-3c) adduct (a-3) of a reactant of a saturated carboxylic acid (a-3b). This additive is also referred to as "modified epoxy resin (a-3)".
Further, in the specification and the patent application of the present application, a compound which belongs to the above definition and does not belong to the above resin (a-1) having a Cardo structure is used as the modified epoxy resin (a-3).

Hereinafter, the epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described.

<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. It is preferably an aromatic epoxy compound having an aromatic group.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a difunctional or higher polyfunctional epoxy compound, 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, and naphthalene type. Bifunctional epoxy resin such as epoxy resin and biphenyl type epoxy resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidylamino diphenylmethane and triglycidyl a glycidylamine type epoxy resin such as a base-p-aminophenol, a tetraglycidyl meta-xylylenediamine, and a tetraglycidyl bisaminomethylcyclohexane; a heterocyclic type such as a triglycidyl isocyanurate; Epoxy resin; phloroglucin triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-epoxy) Propoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-double [ 4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1 3-functional epoxy resin such as -methylethyl]phenyl]ethyl]phenoxy]-2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, four A tetrafunctional epoxy resin such as glycidyl benzophenone, bis resorcinol tetraglycidyl ether or tetraglycidoxybiphenyl.

Further, the epoxy compound (a-3a) is preferably an epoxy compound having a biphenyl skeleton.
The epoxy compound having a biphenyl skeleton preferably has at least one or more biphenyl skeleton represented by the following formula (a-3a-1) in the 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 which can form a cured film excellent in adhesion to a substrate.

[化10]

(In the formula (a-3a-1), R ^{a7 is} independently a hydrogen atom, an alkyl group having 1 or more and 12 or less carbon atoms, a halogen atom or a phenyl group which may have a substituent, and j is 1 or more and 4 or less. Integer)

In the case where R ^a7 is an alkyl group having 1 or more and 12 or less carbon atoms, specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , second butyl, tert-butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, Trioctyl, n-decyl, isodecyl, n-decyl, isodecyl, n-undecyl and n-dodecyl.

In the case where 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 a phenyl group which may have a substituent, the number of the substituent on the phenyl group is not particularly limited. The number of substituents on the phenyl group is from 0 to 5, preferably from 0 or 1.
Examples of the substituent include an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, an aliphatic fluorenyl group having 2 or more and 4 or less carbon atoms, and a halogen atom. , cyano and nitro.

The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, and examples thereof include an epoxy represented by the following formula (a-3a-2). Compound.
[11]

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

Among the epoxy compounds represented by the formula (a-3a-2), the photosensitive composition having excellent balance between sensitivity and developability is particularly preferable, and the following formula (a-3a-3) is preferred. ) the compound represented.
[化12]

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

(Unsaturated carboxylic acid (a-3b))
When the modified epoxy compound (a-3) is prepared, 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 alkyl fluorenyl group or a methacryl fluorenyl group in the molecule. Examples of such an unsaturated group-containing carboxylic acid include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-mercaptoacrylic acid, α-cyanocinnamic acid, and cinnamic acid. Further, the unsaturated group-containing carboxylic acid (a-3b) may be used singly or in combination of two or more.

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

The ratio of the amount of the two of the reactions of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) to the epoxy equivalent of the epoxy compound (a-3a) The ratio of the carboxylic acid equivalent of the saturated carboxylic acid (a-3b) is usually preferably from 1:0.5 to 1:2, more preferably from 1:0.8 to 1:1.25, still more preferably from 1:0.9 to 1: 1.1.
When the ratio of the amount of the epoxy compound (a-3a) to the amount of the unsaturated group-containing carboxylic acid (a-3b) used is from 1:0.5 to 1:2 in the above equivalent ratio, crosslinking efficiency is improved. The tendency is better.

(polybasic anhydride (a-3c))
The polybasic acid anhydride (a-3c) is an acid anhydride of a carboxylic acid having two or more carboxyl groups.
The polybasic acid anhydride (a-3c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic acid. Formic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrohydride Phthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, the following A compound represented by the formula (a-3c-1) and a compound represented by the following formula (a-3c-2). Further, the polybasic acid anhydride (a-3c) may be used singly or in combination of two or more.

[Chemistry 13]

(In the formula (a-3c-2), R ^a8 represents an alkylene group which may have a substituent having 1 or more and 10 or less carbon atoms)

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings from the viewpoint of easily obtaining a photosensitive composition excellent in balance between sensitivity and developability. Further, the polybasic acid anhydride (a-3c) preferably 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).

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and reacting with the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.
Further, as the usage ratio, the number of moles of the OH group and the polybasic acid anhydride (a-3c) in the component after the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) The equivalent ratio of the acid anhydride group 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 acquire the photosensitive composition which is excellent in developability.

Further, 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, based on the resin solid content component. the following. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility to the developer can be obtained, and by setting the acid value to 150 mgKOH/g or less, sufficient hardenability can be obtained, and surface properties can be obtained. Becomes good.

Further, the weight average molecular weight of the modified epoxy resin (a-3) is preferably 1,000 or more and 40,000 or less, more preferably 2,000 or more and 30,000 or less. When the weight average molecular weight is 1000 or more, it is easy to form a cured film excellent in heat resistance and strength. Further, by setting it to 40,000 or less, it is easy to obtain a photosensitive composition which exhibits sufficient solubility to the developer.

[Acrylic resin (a-4)]
The acrylic resin (a-4) is also preferably used as a component constituting the alkali-soluble resin (A).
As the acrylic resin (a-4), a resin containing a constituent unit derived from (meth)acrylic acid and/or a constituent unit derived from another monomer such as (meth)acrylate can be used. (Meth)acrylic acrylic or methacrylic acid. The (meth) acrylate is a compound represented by the following formula (a-4-1), and is not particularly limited as long as the object of the present invention is not impaired.

[Chemistry 14]

In the above formula (a-4-1), R ^a9 is a hydrogen atom or a methyl group, and R ^a10 is a monovalent organic group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

The substituent other than the hydrocarbon group in the organic group of R ^a10 is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, a thiol group, a thio group, a cyano group, an isocyano group, and a cyanate group. , isocyanato group, thiocyanate group, isothiocyanate group, decyl group, decyl alcohol group, alkoxy group, alkoxycarbonyl group, amine methyl group, thioamine formazan group, nitrate Base, nitroso, carboxyl, carboxylate, sulfhydryl, decyloxy, sulfinate, sulfo, sulfonato group, phosphino, phosphinyl, phosphonate, phosphonate (phosphonato group), hydroxyimino group, alkyl ether group, alkyl sulfide group, aryl ether group, aryl sulfide group, amine group (-NH ₂ , -NHR, -NRR': R and R' respectively Independently means a hydrocarbon group). The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of a linear chain, a branched chain, and a cyclic group.

Further, the organic group of R ^a10 may have a reactive functional group such as an acryloxy group, a methacryloxy group, an epoxy group or an oxetanyl group.
A mercapto group having an unsaturated double bond such as an acryloxy group or a methacryloxy group can be, for example, an unsaturated carboxylic acid such as acrylic acid or methacrylic acid and an acrylic resin containing a constituent unit having an epoxy group (a) -4) At least a portion of the epoxy groups are reacted to produce.

As R ^a10 , an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group is preferred, and these groups may be substituted by a halogen atom, a hydroxyl group, an alkyl group or a heterocyclic group. Further, in the case where the groups contain an alkylene moiety, the alkyl group 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 of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and still more preferably 1 or more and 10 or less. Preferred examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-pentyl group and isopentyl group. , second amyl, third amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-decyl, isodecyl, n-decyl, isoindole Base.

In the case where the alkyl group is an alicyclic group or a group containing an alicyclic group, as the preferred alicyclic group contained in the alkyl group, a monocyclic alicyclic ring such as a cyclopentyl group or a cyclohexyl group may be mentioned. a polycyclic alicyclic group such as an adamantyl group, a norbornyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group or a tetracyclododecyl group.

Specific examples of the compound represented by the formula (a-4-1) in the case where the compound represented by the formula (a-4-1) has a chain group having an epoxy group as R ^a10 may be mentioned; Glycidyl acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. Base) Acrylic alkyl acrylates.

Further, the compound represented by the formula (a-4-1) may be an alicyclic epoxy group-containing (meth) acrylate. The alicyclic group constituting the alicyclic epoxy group may be a single ring or a polycyclic ring. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Specific examples of the case where the compound represented by the formula (a-4-1) is an alicyclic epoxy group-containing (meth) acrylate, for example, the following formula (a-4-1a) to (a) Compound represented by a-4-1o). Among these, in order to make the developability into an appropriate range, the compound represented by the following formula (a-4-1a) to (a-4-1e) is preferable, and the following formula (a-) is more preferable. a compound represented by 4-1a) to (a-4-1c).

[化15]

[Chemistry 16]

[化17]

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less carbon atoms, and R ^a22 represents a divalent hydrocarbon group having 1 or more and 10 or less carbon atoms, and An integer of 0 or more and 10 or less is represented. As R ^a21 , a linear or branched alkyl group such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, pentamethylene or hexamethylene is preferred. base. As R ^a22 , for example, a methylene group, an ethyl group, a propyl group, a tetramethylene group, an ethyl group ethyl group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexyl group, and a -CH are preferable. ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

Further, the acrylic resin (a-4) may be a copolymer obtained by further polymerizing a monomer other than (meth) acrylate. Examples of the monomer other than the (meth) acrylate include (meth) acrylamide, an unsaturated carboxylic acid, an allyl compound, a vinyl ether, a vinyl ester, and a styrene. These monomers may be used singly or in combination of two or more.

Examples of the (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, and N, N-di. Alkyl (meth) acrylamide, N,N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N- Base (meth) acrylamide and the like.

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

Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, Allyl acetate such as allyl acetate, allyl lactate; allyloxyethanol and the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, and chloroethyl vinyl ether. 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethyl Alkyl vinyl ethers such as aminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl toluene ether, vinyl chlorophenyl ether, vinyl a vinyl aryl ether such as 2,4-dichlorophenyl ether, vinyl naphthyl ether or vinyl anthracene.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, and dichloro Vinyl acetate, methoxyvinyl acetate, butoxy vinyl acetate, vinyl phenyl acetate, ethylene vinyl acetate, vinyl lactate, vinyl β-phenylbutyrate, vinyl benzoate, water Vinyl acetate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate, and the like.

Examples of the styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, and butylstyrene. Alkenyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl methyl styrene Alkoxystyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; chlorostyrene, dichlorostyrene, trichlorostyrene, Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3 - Halogenated styrene such as trifluoromethylstyrene.

The amount of the constituent unit derived from (meth)acrylic acid in the acrylic resin (a-4) and the amount of the constituent unit derived from the other monomer are not particularly limited as long as the object of the present invention is not impaired. The amount of the constituent unit derived from (meth)acrylic acid in the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less, more preferably the mass of the acrylic resin (a-4). It is 10% by mass or more and 30% by mass or less.

In the case where the acrylic resin (a-4) has a constituent unit having an unsaturated double bond, the amount of the constituent unit having an unsaturated double bond in the acrylic resin (a-4) is preferably 1% by mass or more. 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less.
When the acrylic resin (a-4) contains a constituent unit having an unsaturated double bond in an amount within the above range, the crosslinking reaction of the acrylic resin into the resist film can be uniformized, so that the cured film is The improvement of heat resistance and mechanical properties is effective.

The weight average molecular weight of the acrylic resin (a-4) is preferably 2,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less. When it is set to the above range, there is a tendency to easily obtain a balance between the film forming ability of the photosensitive composition and the developability after exposure.

The content of the alkali-soluble resin (A) is preferably 10% by mass or more and 65% by mass or less, and more preferably 15% by mass or more and 50% by mass or less based on the total mass of the solid content component of the photosensitive composition. By setting it as the said range, the photosensitive composition excellent in developability is acquired easily.

<Photopolymerizable monomer (B)>
As the photopolymerizable monomer (B), a compound having an ethylenically unsaturated double bond can be preferably used. Preferred examples of the compound having an ethylenically unsaturated double bond include a monofunctional monomer and a polyfunctional monomer.

Examples of the monofunctional monomer include (meth)acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl). Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyl Base (meth) acrylamide, (meth) acrylate, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, butyl Acrylic acid, 2-propenylamine-2-methylpropanesulfonic acid, tert-butyl propylene decyl sulfonic 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, (meth)acrylic acid 2 -hydroxybutyl ester, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylic acid Ester, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (methyl) propyl Acid glycidyl ester, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth) Acrylic acid half ester and the like. These monofunctional monomers may be used singly or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol. Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 1,12-dodecanediol di(a) Acrylate, ethoxylated hexanediol di(meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, 2-hydroxy-3-(methyl) acrylate (meth) acrylate醯-propyl propyl ester, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(methyl) Acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, C Oxylated ethoxylated bisphenol A di(meth) acrylate, ethylene glycol di(meth) propylene Ester, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol II Methyl) acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, glycerol di(a) Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (methyl) ) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis(4-(methyl) propylene oxy diethoxy phenyl) propane, 2 , 2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth)acrylate, ethylene glycol II Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(methyl) Acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, (meth) acrylate urethane (ie, toluene diisocyanate, trimethyl hexamethylene diisocyanate or six a reaction product such as methylene diisocyanate with 2-hydroxyethyl (meth)acrylate), methylene bis(meth) acrylamide, (meth) acrylamide methyl ether, polyol and N a condensate of hydroxymethyl (meth) acrylamide, tripropylene decyl formal, 2,4,6-trisethoxy hexahydro-1,3,5-tris-1,3,5- Triethanol triacrylate and 2,4,6-trisethoxy hexahydro-1,3,5-tris-1,3,5-triethanol diacrylate. These polyfunctional monomers may be used singly or in combination of two or more.

Among these compounds having an ethylenically unsaturated double bond, a difunctional or higher polyfunctional monomer is preferred in terms of obtaining a photosensitive composition which provides a cured product having excellent strength and adhesion to a substrate. Among these, a trifunctional or higher polyfunctional monomer is particularly preferable. For example, pentaerythritol tetrakis(meth)acrylate (tetrafunctional monomer), dipentaerythritol penta(meth)acrylate (pentafunctional monomer), and dipentaerythritol hexa(meth)acrylate (hexafunctional monomer) can be preferably used. ).
From the viewpoint of controlling the glass transition point (Tg), a monofunctional monomer or a difunctional monomer may be used in combination with a trifunctional or higher polyfunctional monomer, among which 1,6-hexane is preferred. Alcohol di(meth)acrylate.

The content of the photosensitive composition of the photopolymerizable monomer (B) is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more based on the total mass of the solid content component of the photosensitive composition. And 40% by mass or less. By setting it as the said range, it exists in the tendency to acquire the balance of sensitivity, developability, and resolution.

<Photopolymerization initiator (C)>
The photosensitive composition contains the oxime ester compound (C1) represented by the following formula (c1) as a photopolymerization initiator (C). Hereinafter, the oxime ester compound (C1) will be described.

[肟 ester compound (C1)]
The oxime ester compound (C1) is represented by the following formula (c1):
[化18]

(In the formula (c1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, R ³ is a monovalent organic group, and R ⁴ is a monovalent organic group. R ⁵ and R ⁶ are each independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and m1, m2 and m3 are each 0 or 1),
And a compound satisfying at least one of the following (1) to (3):
(1) R ¹ contains a group represented by -OR ⁷ and R ⁷ is a haloalkyl group.
(2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.

In the formula (c1), R ⁵ and R ⁶ are a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
The ring containing the nitrogen atom to which R ³ is bonded as shown in the formula (c1) is condensed with a benzene ring or a naphthalene ring by a carbon-carbon bond in a common benzene ring or a naphthalene ring.
Therefore, the ring containing the nitrogen atom to which R ³ is bonded in the formula (c1) is a member of a ring of nitrogen atoms, two carbon atoms derived from R ⁵ and two carbon atoms derived from R ⁶ . ring.
That is, the compound represented by the formula (c1) contains R ⁵ and R ⁶ and the above 5-membered ring, and has a 3-ring to 5-ring condensed ring as a central skeleton.

In the case where R ⁵ and/or R ⁶ is a naphthalene ring, the condensation form of the above 5-membered ring and the naphthalene ring containing a nitrogen atom bonded to R ³ is not particularly limited.
In the case where at least one of R ⁵ and R ⁶ is a naphthalene ring, the condensed ring containing the above 5-membered ring containing R ⁵ and R ⁶ and a nitrogen atom bonded to R ³ may be any of the following.
[Chemistry 19]

In the case where the benzene ring or the naphthalene ring of R ⁵ and R ⁶ has a substituent, the kind and the number of the substituent are not particularly limited as long as the object of the present invention is not impaired.
Preferable examples of the substituent include an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, and a saturated aliphatic fluorenyl group having 2 or more and 7 or less carbon atoms. And an alkoxycarbonyl group having 2 or more and 7 or less carbon atoms, a saturated aliphatic decyloxy group having 2 or more and 7 or less carbon atoms, a monoalkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, A dialkylamino group, a porphyrin-1-yl group, a piperidin-1-yl group, a halogen atom, a cyano group or the like having an alkyl group having 1 or more and 6 or less carbon atoms.
In the case where the benzene ring or the naphthalene ring of R ⁵ and R ⁶ has a substituent, the number of the substituent is not limited insofar as it does not impair the object of the present invention, and is preferably 1 or more and 4 or less. In the case where the substituent is plural, the plurality of substituents may be the same or different.

When R ⁵ in the case of having a substituent of the group, R ⁵ substituents may be possessed by the R ¹ or R ³ bonded to form a ring.
Further, in the case where R ⁶ has a substituent of the group, R ⁶ has a substituent of R ³ may be bonded to form a ring.

The ring formed by the substituent of R ⁵ and R ¹ may be a hydrocarbon ring or a hetero ring. The hetero atom contained in the hetero ring is not particularly limited. Preferred examples of the hetero atom include N, O, and S.
R ⁵ and / or R ⁶ has the substituents R ³ bonded to form a ring other than the nitrogen atom bonded to the R ^3, may also contain other hetero atoms. The hetero atom contained in the hetero ring is not particularly limited. Preferred examples of the hetero atom include N, O, and S.

When the substituent of R ⁵ or the substituent of R ⁶ is bonded to R ³ to form a ring, the compound represented by formula (c1) is preferably the following formula (c1-1-a). ) to (c1-1-h) the compound represented:
[Chemistry 20]

(In the formulae (c1-1-a) to (c1-1-h), R ¹ , R ² , R ⁴ , m1, m2 and m3 are the same as those of the formula (c1), and R ⁸ is an alkyl group).

The alkyl group as R ⁸ may be linear or branched. The number of carbon atoms of the alkyl group of R ⁷ is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less.

In the case where the substituent of R ⁵ is bonded to R ¹ to form a ring, in the formula (c1), m1 is preferably 0. In this case, the compound represented by the formula (c1) is preferably a compound represented by the following formulas (c1-1-i) to (c1-1-1):
[Chem. 21]

(In the formulae (c1-1-i) to (c1-1-1), R ² , R ³ , R ⁴ , m2 and m3 are the same as the formula (c1), and R ⁸ is a carbon number of 1 or more and 20 or less. alkyl).
The alkyl group as R ⁸ may be linear or branched.

In view of the preferred combination of R ⁵ and R ⁶ described above, the compound represented by the formula (c1) is preferably a compound represented by the following formulas (c1 - I) to (c1 - IV):
[化22]

(In the formulae (c1-I) to (c1-IV), R ¹ , R ² , R ³ , R ⁴ , m1, m2 and m3 are the same as in the formula (c1)),
More preferably, it is a compound represented by the formula (c1-II) or the formula (c1-III), and particularly preferably a compound represented by the formula (c1-III).

The compound represented by the above formulas (c1 - I) to (c1 - IV) is preferably a compound represented by the following formulas (c1 - Ia) to (c1 - IV - a), more preferably a formula (c1). The compound represented by II-a) or formula (c1-III-a) is particularly preferably a compound represented by formula (c1-III-a).
[化23]

The compound represented by the above formulas (c1 - Ia) to (c1 - IV - a) is preferably a compound represented by the following formulas (c1 - Ib) to (c1 - IV - b), more preferably a formula ( The compound represented by the formula (c1-II-b) or the formula (c1-III-b) is particularly preferably a compound represented by the formula (c1-III-b).
[Chem. 24]

As an example of the preferred monovalent organic group as R ¹ , an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyloxy group may be mentioned. a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyl methoxy group which may have a substituent, a phenylalkyl group having a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, may have a substituent Naphthylmethoxycarbonyl, naphthylalkyl group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl group which may have a substituent, amine group substituted by one or two organic groups, hydrazine Andolin-1-yl and piperidin-1-yl and the like.

When R ¹ is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, in the case where R ¹ is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ¹ is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, and n-pentyl group. Base, isopentyl, second pentyl, third amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-decyl, isodecyl, positive Sulfhydryl and isomeric groups. Further, in the case where R ¹ is an alkyl group, the alkyl group may have an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxy group. Ethoxyethyl and methoxypropyl and the like.

When R ¹ is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, in the case where R ¹ is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ¹ is an alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, trioctyloxy, n-decyloxy, isodecyloxy, n-decyloxy and isodecyloxy. Further, in the case where R ¹ is an alkoxy group, the alkoxy group may have an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Base, propoxyethoxyethoxy and methoxypropoxy groups, and the like.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of the case where R ¹ is 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 the case where R ¹ is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms of the saturated aliphatic fluorenyl group or the saturated aliphatic fluorenyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more. And 7 or less. Specific examples of the case where R ¹ is a saturated aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, a n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, a n-pentamethylene group, and a 2,2-dimethyl group. Propyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-decyl fluorenyl group, n-dodecyl fluorenyl group, n-tridecyl fluorenyl group, positive fourteen Carbon sulfhydryl, n-pentadecacarbonyl and n-hexadecanthyl. Specific examples of the case where R ¹ is a saturated aliphatic fluorenyloxy group include an ethoxycarbonyl group, a propenyloxy group, a n-butenyloxy group, a 2-methylpropoxy group, and a n-pentyloxy group. , 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy, N-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy and n-hexadecyloxy.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of the case where R ¹ is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, and an isobutoxy group. Carbonyl, second butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, second pentyloxycarbonyl, third pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy Carbocarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, n-decyloxycarbonyl and isodecyloxy Alkylcarbonyl and the like.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Further, when R ¹ is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of the case where R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ¹ is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl group). ) Ethyl. In the case where R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or a naphthyl group.

In the case where R ¹ is a heterocyclic group, the heterocyclic group is a monocyclic ring containing 5 or more members of N, S or O, or the monocyclic ring or the monocyclic ring is condensed with the benzene ring. A heterocyclic group. In the case where the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridinium, pyrimidine, and the like. Bismuth, benzofuran, benzothiophene, anthracene, isoindole, anthracene , benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quinazoline, anthracene, porphyrin and quinoxaline. In the case where R ¹ is a heterocyclic group, the heterocyclic group may further have a substituent.

In the case where R ¹ is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where R ¹ is a heterocyclic group.

In the case where R ¹ is an amine group substituted with one or two organic groups, examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, and a carbon number of 3 or more and 10 or less. a cycloalkyl group, a saturated aliphatic fluorenyl group having 2 or more and 21 or less carbon atoms, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, and a carbon atom having a substituent of 7 or more and 20 or less A phenylalkyl group, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such preferred organic groups are the same as those of R ¹ . Specific examples of the amine group substituted with one or two organic groups include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, and a different one. Propylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamine, n-decyl Amino, phenylamino, naphthylamino, etidylamino, propylamino, n-butyl decyl, n-pentylamino, n-hexylamino, n-heptylamino, A n-octylamino group, a n-decylamino group, a benzhydrylamino group, an α-naphthylmethylamino group, and a β-naphthylmethylamino group.

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ have a substituent include an alkyl group having 1 or more and 6 or less carbon atoms, and a carbon number of 1 or more and 6 or less. Alkoxy group, a saturated aliphatic fluorenyl group having 2 or more and 7 or less carbon atoms, an alkoxycarbonyl group having 2 or more and 7 or less carbon atoms, a saturated aliphatic decyloxy group having 2 or more and 7 or less carbon atoms, a monoalkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a dialkylamino group having an alkyl group having 1 or more and 6 or less, porphyrin-1-yl, and piperidin-1- Base, halogen, nitro and cyano groups. In the case where the phenyl group, the naphthyl group and the heterocyclic group contained in R ¹ further have a substituent, the number of the substituent is not limited insofar as it does not impair the object of the present invention, and is preferably 1 or more and 4 the following. When the phenyl group, the naphthyl group and the heterocyclic group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Further, R ^{1 is} preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The phenoxyalkyl group and the phenylthioalkyl group may have the same substituent as the substituent which the phenyl group contained in R ¹ may have.

Among the monovalent organic groups, R ^{1 is} preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring. . The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, and still more preferably an alkyl group having 1 or more and 4 or less carbon atoms. Good for methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of 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 still more preferably 5 or 6. The number of carbon atoms of 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 of the alkylene group contained in the phenylthioalkyl group having 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 still more preferably 2 or less. Among the phenylthioalkyl groups having a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferred.

As described above, the compound represented by the formula (c1) must satisfy at least one of the following conditions (1) to (3):
(1) R ¹ contains a group represented by -OR ⁷ and R ⁷ is a haloalkyl group.
(2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
Therefore, R ^{1 is} preferably substituted with a substituent represented by -OR ⁷ . R ⁷ is a haloalkyl group. The substituents on the group R & lt -OR ¹ through ⁷ represent the case of, R ¹ -OR number contained in the group represented by the sum ⁷ is not particularly limited. By -OR ¹ when R & lt on the substituent of the group represented by the case ^7, R ¹ -OR number contained in the group represented by the ^seven of preferably 1 or 2, more preferably 1.
Further, the number of the groups represented by -OR ⁷ of the compound represented by the formula (c1) is also preferably 1 or 2, more preferably 1.

Examples of the halogen atom contained in the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The haloalkyl group may contain one halogen atom or may contain two or more kinds of halogen atoms in combination.
The number of the halogen atoms which the haloalkyl group has is not particularly limited insofar as it does not impair the object of the present invention. The number of halogen atoms which the haloalkyl group has is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit of the number of halogen atoms in the haloalkyl group is preferably 7 or less, and more preferably 7 or less, in terms of compatibility between the compound represented by the formula (c1) and other components in the photosensitive composition. It is 6 or less, and particularly preferably 5 or less.
Further, the number of halogen atoms contained in the compound represented by the formula (c1) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, more preferably 7 or less, still more preferably 6 or less. It is especially good for 5 or less.

The number of carbon atoms of the haloalkyl group is not particularly limited insofar as it does not impair the object of the present invention. The number of carbon atoms of the haloalkyl group is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit of the number of carbon atoms of the haloalkyl group is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less.
As the haloalkyl group, a fluorinated alkyl group is preferred. Preferred examples of the haloalkyl group include 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2, 2,3,3,3-pentafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl and the like. Among these, the compound represented by the formula (c1) is preferably easily produced, and is preferably 2,2,3,3-tetrafluoropropyl.

As the halogen-substituted alkyl group as R ¹ , a phenyl group substituted by one or two haloalkyl groups is preferred. Specifically, the halogen-substituted alkyl group as R ¹ is preferably a group represented by the following formula (c1-01):
[化25]

(In the formula (c1-01), R ^{7 is} as defined above, and R ⁹ is a substituent which the phenyl group as R ¹ may have, m4 is 1 or 2, and m4+m5 is an integer of 1 or more and 5 or less).
R ^{9 is} preferably an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, more preferably an alkyl group having 1 or more and 6 or less carbon atoms, and further more preferably Preferably, it is a methyl group and an ethyl group, and particularly preferably a methyl group.
M5 is preferably 1.

Further, R ¹ may be a group represented by the following formula (c1-02):
[Chem. 26]

(In the formula (c1-02), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m1, m2 and m3 are the same as those of the formula (c1), and R ¹⁰ is a divalent organic group).

R ^{10 is} the divalent organic based not particularly limited within the range does not impair the object of the present invention. Preferable examples of the divalent organic group as R ¹⁰ include an alkanediyl group having 1 or more and 10 or less carbon atoms (for example, methylene, ethane-1,2-diyl, propane-1,3). -diyl, butane-1,4-diyl, etc.) and aryl (p-phenyl, meta-phenyl, o-phenyl, 1,1'-biphenyl-4,4' diyl, etc. ).

Specific examples of the compound represented by the formula (c1) in the case where R ¹ is a group represented by the above formula (c1-02) include a compound of the following formula.
[化27]

Among R ¹ described above, a group represented by the following formula is preferred.
[化28]

In the formula (c1), R ² is a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. The hydrocarbon group which may have a substituent is preferably an alkyl group having 1 or more and 11 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the aryl group, a phenyl group and a naphthyl group are preferred, and a phenyl group is preferred. The substituent which may be contained in the case where R ² is an alkyl group is preferably a phenyl group, a naphthyl group or the like. Further, the substituent which may be contained in the case where R ² is an aryl group is preferably an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom or the like.

In the case where R ² is a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. In the case where R ² is a heterocyclic group, the heterocyclic group is a monocyclic ring containing 5 or more members of N, S or O, or the monocyclic ring or the monocyclic ring is condensed with the benzene ring. A heterocyclic group. In the case where the heterocyclic group is a condensed ring, the number of rings is at most 3. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridinium, pyrimidine, and the like. Bismuth, benzofuran, benzothiophene, anthracene, isoindole, anthracene Benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quinazoline, indole, porphyrin, quinoxaline, piperidine, piperidine , porphyrin, piperidine, tetrahydropyran and tetrahydrofuran.
In the case where R ² is a heterocyclic group, examples of the substituent which the heterocyclic group may have include a hydroxyl group, an alkoxy group having 1 or more and 6 or less carbon atoms, a halogen atom, a cyano group, a nitro group and the like.

R ^{2 is} preferably a methyl group, a phenyl group or a thienyl group, more preferably a methyl group.

In the formula (c1), R ³ is a monovalent organic group. R ³ can be selected from various organic groups within the range not impairing the object of the present invention. Preferable examples of R ³ include an alkyl group which may have a substituent of 1 or more and 20 or less carbon atoms, a cycloalkyl group which may have a substituent of 3 or more and 20 or less carbon atoms, and 2 carbon atoms. a saturated aliphatic fluorenyl group which may have a substituent of 20 or more, an alkoxycarbonyl group which may have a substituent of 2 or more and 20 or less, a phenyl group which may have a substituent, and a phenyl group which may have a substituent a mercapto group, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 or more and 20 or less carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, A naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent.

Among R ³ , an alkyl group having 1 or more and 20 or less carbon atoms is preferred. The alkyl group may be linear or branched. When the solubility of the compound represented by the formula (c1) in the photosensitive composition is good, the number of carbon atoms of the alkyl group as R ³ is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 the above. In addition, in the photosensitive composition, the compatibility of the compound represented by the formula (c1) with other components is good, and the number of carbon atoms of the alkyl group as R ³ is preferably 15 or less, more preferably 10 or less. .

In the case where R ³ has a substituent, examples of the substituent include a hydroxyl group, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and carbon. An aliphatic fluorenyl group having 2 or more and 20 or less atoms, an aliphatic decyloxy group having 2 or more and 20 or less carbon atoms, a phenoxy group, a benzylidene group, a benzamethyleneoxy group, or a -PO(OR) ₂ group The group represented by R (R is an alkyl group having 1 or more and 6 or less carbon atoms), a halogen atom, a cyano group or a heterocyclic group. Preferred examples of the heterocyclic group as a substituent are the same as preferred examples of the heterocyclic group as R ² .

As described above, the compound represented by the formula (c1) must satisfy at least one of the following conditions (1) to (3):
(1) R ¹ contains a group represented by -OR ⁷ and R ⁷ is a haloalkyl group.
(2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
Therefore, R ^{3 is} preferably a branched alkyl group which may have a substituent.

Further, as R ³ , it is the following formula (c1-03):
[化29]

(In the formula (c1-03), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , m1, m2 and m3 are the same as the formula (c1), and R ¹¹ is a divalent organic group)

As the divalent organic R ¹¹ is not particularly limited within a range based on the object of the present invention are not impaired. Preferred examples of the divalent organic group as R ¹¹ include an alkanediyl group having 1 or more and 10 or less carbon atoms (for example, methylene, ethane-1,2-diyl, propane-1,3). -diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8 - Diyl, etc.), aryl (p-phenyl, meta-phenyl, o-phenyl, 1,1'-biphenyl-4,4' diyl, etc.).

Further, as the divalent organic group of R ¹¹ , the following group is also preferable. In the following formula, R ¹² is an alkylene group having 1 or more and 20 or less carbon atoms. As the alkylene group as R ¹² , a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1 are preferable. , 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl and octane-1,8-diyl.
[化30]

Specific examples of the compound represented by the formula (c1) in the case where R ³ is a group represented by the above formula (c1-03) include a compound of the following formula.
[化31]

Preferred examples of R ³ described above include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl. , isoamyl, neopentyl, pentan-3-yl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl.
As described above, R ^{3 is} preferably a branched alkyl group, and therefore, among the above alkyl groups, an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, an isopentyl group, and a new group are preferable. Butyl, pentan-3-yl, second pentyl, third pentyl and 2-ethylhexyl.
Further, the compound represented by the formula (c1) is preferably an n-octyl group and a 2-ethylhexyl group, and more preferably a 2-ethylhexyl group, in terms of solubility in a photosensitive composition.

R ⁴ in the formula (c1) is a monovalent organic group. The monovalent organic group as R ⁴ may be the same as the monovalent organic group as R ¹ .

R ^{4 is} bonded to the main skeleton of the compound represented by the formula (c1) as a group represented by R ⁴ -(CO) _m3 -. Preferred examples of the group represented by R ⁴ -(CO) _m3 - include the groups represented by the following formulas. In the following formula, m3 is 1 or 0 in the same manner as in the formula (c1).
[化32]

[化33]

[化34]

Among the preferred examples of the group represented by the above R ⁴ -(CO) _m3 - , a 1,3,5-trimethylbenzylidene group is preferred.

As described above, the compound represented by the formula (c1) must satisfy at least one of the following conditions (1) to (3):
(1) R ¹ contains a group represented by -OR ⁷ and R ⁷ is a haloalkyl group.
(2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
Therefore, R ^{4 is} preferably substituted with a substituent represented by -OR ⁷ . R ⁷ is a haloalkyl group. Regarding R ⁷ , as described above.

As the halogenated alkyl group substituted by R ⁴ , a phenyl group substituted by one or two haloalkyl groups is preferred. Specifically, similarly to the group substituted with a haloalkyl group as R ¹ , a group represented by the above formula (c1-01) is preferred.

Further, as R ⁴ , the group represented by the following formula (c1-04) is also preferable:
[化35]

(In the formula (c1-04), R ¹ , R ³ , R ⁵ , R ⁶ , m1, m2 and m3 are the same as those of the formula (c1), and R ¹³ is a divalent organic group).

As the divalent organic R ¹³ is not particularly limited within a range based on the object of the present invention are not impaired. Preferable examples of the divalent organic group as R ¹³ include an alkanediyl group and an extended aryl group having 1 or more and 10 or less carbon atoms. Specific examples of the alkanediyl group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. - Diyl, hexane-1,6-diyl, heptane-1,7-diyl and octane-1,8-diyl and the like. Specific examples of the aryl group include a p-phenylene group, an exophenyl group, an o-phenyl group, and a 1,1'-biphenyl-4,4'-diyl group.

Further, as the divalent organic group of R ¹³ , the following group is also preferable. In the following formula, R ¹³ is an alkylene group having 1 or more and 20 or less carbon atoms which may be substituted by a halogen atom. As the alkylene group as R ¹⁴ , a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1 group are preferable. 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl and octane-1,8-diyl.
Further, as R ¹⁴ , all of the hydrogen atoms in the alkylene group are substituted with a halogen atom, and a group substituted with a fluorine atom is also preferable.
[化36]

In the formula (c1), m1, m2 and m3 are both 0 or 1. As m1, it is preferably 0. As m2, it is preferably 1, and as m3, it is preferably 1.

Preferred examples of the compound represented by the formula (c1) described above include the following compounds.
[化37]

[化38]

[39]

[化40]

[化41]

[化42]

[化43]

As described above, the compound represented by the formula (c1) must satisfy at least one of the following conditions (1) to (3):
(1) R ¹ contains a group represented by -OR ⁷ and R ⁷ is a haloalkyl group.
(2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent. If this condition is satisfied, two or more different compounds may be mixed and used as a photopolymerization initiator (C).

As described above, the photosensitive composition contains the oxime ester compound (C1) as a photopolymerization initiator (C). The oxime ester compound (C1) is excellent in the ability to absorb ultraviolet rays and generate radicals. Therefore, the oxime ester compound (C1) is highly sensitive, and even when it contains a high concentration of the light-shielding agent (D), it is easy to sufficiently harden the photosensitive composition with a small amount of exposure. In the case of a photosensitive composition containing a large amount of the opacifier (D), when the optical density of the film forming the photosensitive composition is 3, the ultraviolet exposure amount of the deep portion is one thousandth of the surface portion (the outermost surface). When the optical density is 4, it will become one ten thousandth of the surface layer (the outermost surface), and the oxime ester compound (C1) can generate radicals even with such a relatively small amount of ultraviolet exposure, thereby making the photosensitive combination The material hardens well.

In the case where the following light-shielding agent (D) is blended at a high concentration in the photosensitive composition, the coating film containing the photosensitive composition inevitably generates a primary aggregate of the light-shielding agent (D) (coagulation) body). However, in the case of using a photosensitive composition containing the oxime ester compound (C1) as the photopolymerization initiator (C), the photopolymerization initiator (C) can be used even if the agglomerates are complicatedly overlapped by a little bit gap. Free radicals are generated upon exposure to ultraviolet light.
As a result, the cured product of the photosensitive composition is excellent not only in the environment of normal temperature and humidity but also in an atmospheric pressure, and is excellent in adhesion to a substrate or electrical resistivity (insulating property) even when the cured product is exposed to a high-temperature, high-humidity, high-pressure environment. The adhesion to the substrate or the resistivity (insulation) are not easily lowered. The durability in a high-temperature, high-humidity, high-pressure environment can be confirmed by a so-called PCT test (Pressure Cooker Test).
Therefore, in the image display panel using the black matrix containing the cured product containing the photosensitive composition of the oxime ester compound (C1), even if the use environment is high temperature or high humidity, performance degradation is less likely to occur.

The photopolymerization initiator (C) may contain a photopolymerization initiator other than the oxime ester compound (C1) within a range not impairing the object of the present invention. The ratio of the mass of the oxime ester compound (C1) to the mass of the photopolymerization initiator (C) as a whole is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass or more. It is 40% by mass or more.

As the photopolymerization initiator (C) other than the oxime ester compound (C1), for example, an aminoalkylphenone-based photopolymerization initiator (C2) can be preferably used.
A preferred example of the aminoalkylphenone-based photopolymerization initiator (C2) is a compound represented by the following formula (c2-1).

[化44]

In the formula (c2-1), R ^c01 is a linear, branched or cyclic alkyl group having 1 or more and 12 or less carbon atoms.
R ^c02 and R ^c03 are each independently a hydrogen atom, an alkyl group having 1 or more and 12 or less carbon atoms, or a cycloalkyl group or a benzyl group having 3 or more and 12 or less carbon atoms. The alkyl group as R ^c02 or R ^c03 may be linear or branched.
R ^c04 , R ^c05 , R ^c07 and R ^c08 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 12 or less carbon atoms, a cycloalkyl group having 3 or more and 12 or less carbon atoms or a carbon number of 1 or more. And an alkoxy group of 4 or less. The alkyl group and the alkoxy group as R ^c04 , R ^c05 , R ^c07 and R ^c08 may be linear or branched.
R ^c06 is a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 12 or less carbon atoms, a cycloalkyl group having 3 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 4 or less carbon atoms. The alkyl group and the alkoxy group of R ^c06 may be linear or branched. Further, the alkyl group, the cycloalkyl group and the alkoxy group of R ^c06 may be substituted with one or more substituents. The substituent is one or more selected from the group consisting of a hydroxyl group and an alkoxy group having 1 or more and 4 or less carbon atoms. The alkoxy group as a substituent in R ^c06 may be linear or branched.

Preferred examples of the case where R ^c01 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and t-butyl groups. N-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl and n-dodecyl groups. Among these, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, a n-pentyl group and a n-hexyl group are preferred, and more preferably Ethyl.

Preferable examples of the case where R ^c01 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclodecyl group, Cyclodecyl and cyclododecyl.

Preferred examples of the case where R ^c02 and R ^c03 are an alkyl group or a cycloalkyl group are the same as those in the case where R ^c01 is an alkyl group or a cycloalkyl group. R ² O ² and R ^{c03 are} preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, n-hexyl, or Heptyl and n-octyl, more preferably methyl.

Specific examples of the case where R ^c04 , R ^c05 , R ^c07 and R ^c08 are a halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom.
Preferred examples of the case where R ^c04 , R ^c05 , R ^c07 and R ^c08 are an alkyl group or a cycloalkyl group are the same as those in the case where R ^c01 is an alkyl group or a cycloalkyl group.
Specific examples of the case where R ^c04 , R ^c05 , R ^c07 and R ^c08 are alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and the like. Butoxy, second butoxy and third butoxy.
R ^c04 , R ^c05 , R ^c07 and R ^c08 are preferably hydrogen atoms in terms of a sensitivity and a depth of focus of the photosensitive composition, and a cured film which is easy to form a good adhesion to a substrate. A methyl group and an ethyl group are more preferably a hydrogen atom.

A specific example in the case where R ^c06 is a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group, and a case where R ^c04 , R ^c05 , R ^c07 and R ^c08 are a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group. The specific examples are the same.
^When the alkyl group as R ^c06 or the alkyl group, the cycloalkyl group or the alkoxy group of R ^c06 is substituted with one or more substituents, the substituent is preferably a hydroxyl group or a methoxy group.

Preferred examples of R ^{c06 are} preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, a t-butyl group or a n-pentyl group. , n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, hydroxymethyl, 2-hydroxyethyl, methoxymethyl, 2-methoxyethyl, methoxy, Ethoxy, n-propoxy, isopropoxy, n-butoxy, hydroxymethoxy, 2-hydroxyethoxy, methoxymethoxy and 2-methoxyethoxy, etc., more preferably It is a hydrogen atom, a methyl group and an ethyl group.

Preferably, R ^c01 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl or n-hexyl, and R ^c02 is methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, R ^c03 is methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, etc., R ^c04 is hydrogen An atom, a methyl group or an ethyl group, R ^c05 is a hydrogen atom, a methyl group or an ethyl group, R ^c07 is a hydrogen atom, a methyl group or an ethyl group, R ^c08 is a hydrogen atom, a methyl group or an ethyl group, and R ^c06 is a methyl group or A hydrogen atom.

Examples of the aminoalkylphenone compound represented by the formula (c2-1) include 2-benzyl-2-(dimethylamino)-1-(4-carbolinylphenyl) butyl Alkan-1-one (for example, IRGACURE 369 manufactured by Ciba Specialty Chemicals, Inc.), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)butane- 1-ketone (for example, IRGACURE 379, manufactured by Ciba Specialty Chemicals, Inc.), 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)butane-1- Ketone, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)butan-1-one, 2-(4-n-butylbenzyl) 2-(2-dimethylamino)-1-(4-carbolinylphenyl)butan-1-one, 2-(4-isobutylbenzyl)-2-(dimethylamino) 1-(4-carbolinylphenyl)butan-1-one, 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-carbolinyl) Phenyl)butan-1-one, 2-(3,4-dimethylbenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)butan-1-one , 2-(4-methoxybenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)butan-1-one, 2-(4-ethoxybenzyl) )-2-(dimethylamino)-1-(4-carbolinylphenyl)butan-1-one, 2-(4-hydroxymethylbenzyl)-2-(dimethylamino)- 1-(4-carbolinyl) Phenyl)butan-1-one, 2-[4-(2-hydroxyethoxy)benzyl]-2-(dimethylamino)-1-(4-carbolinylphenyl)butane- 1-keto, 2-[4-(2-methoxyethoxy)benzyl]-2-(dimethylamino)-1-(4-carbolinylphenyl)butan-1-one, 2-(4-Isopropylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-carbolinylphenyl)butan-1-one, 2-(4 -n-butylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-carbolinylphenyl)butan-1-one, 2-(4-isopropyl Benzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)pentan-1-one, 2-(4-isobutylbenzyl)-2-[(n-butyl) (methyl)amino]]-1-(4-carbolinylphenyl)pentan-1-one, 2-(4-n-butoxybenzyl)-2-[(n-butyl)( Methyl)amino]-1-(4-carbolinylphenyl)pentan-1-one, 2-(4-methylbenzyl)-2-[di(n-octyl)amino]-1 -(4-carbolinylphenyl)hexane-1-one and 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl) ) octane-1-one and the like.
Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-carbolinylphenyl)butan-1-one is preferred.

When the aminoalkylphenone-based photopolymerization initiator (C2) is combined with the oxime ester compound (C1), the cross-sectional shape of the black matrix formed using the photosensitive composition can be easily controlled. Specifically, the cross-sectional shape of the black matrix can be changed from the forward cone to the inverted cone by making the following line taper angle with respect to the cross-sectional shape of the black matrix. The shape of the forward taper is the cross-sectional shape shown in Fig. 1 below, and the shape of the inverted taper is the cross-sectional shape shown in Fig. 2 below.

For example, when the photopolymerization initiator (C) is composed only of the oxime ester compound (C1) and the aminoalkylphenone-based photopolymerization initiator (C2), if the aminoalkylphenone is photopolymerized When the amount of the initiator (C2) used is large, the respective θ values shown in FIGS. 1 and 2 become large, and it is easy to form a patterned cured film having a cross-sectional shape of an inverted tapered shape.
On the other hand, when the amount of the oxime ester compound (C1) used is large, the respective θ values shown in FIGS. 1 and 2 become small, and it is easy to form a patterned cured film having a cross-sectional shape of a forward tapered shape.

The reason for this is considered to be that the aminoalkyl phenone-based photopolymerization initiator (C2) tends to relatively generate photopolymerization radicals in the surface layer portion of the photosensitive composition (the surface facing the exposed light and its vicinity). The oxime ester compound (C1) tends to relatively generate photopolymerization radicals in the deep portion of the photosensitive composition. The thicker the film thickness of the photosensitive composition, the more pronounced this tendency is, and the film thickness of 1 μm or less can be confirmed.
Further, as a secondary effect of using an aminoalkylphenone-based photopolymerization initiator (C2) together with the oxime ester compound (C1), the sensitivity is improved comprehensively, and the photosensitive composition can be hardened by a small amount of exposure. Things. Further, when an aminoalkylphenone photopolymerization initiator (C2) is used together with the oxime ester compound (C1), the straightness of the line edge is good with the adhesion to the substrate, and it is easy to form a pattern defect. Black matrix.

In the photosensitive composition, when the photopolymerization initiator (C) contains an oxime ester compound (C1) and an aminoalkylphenone photopolymerization initiator (C2), the aminoalkylphenone light is used. The ratio of the mass of the polymerization initiator (C2) to the total mass of the oxime ester compound (C1) and the mass of the aminoalkylphenone-based photopolymerization initiator (C2) is preferably 20% by mass or more and 75. The mass% or less is more preferably 25% by mass or more and 70% by mass or less, and particularly preferably 30% by mass or more and 60% by mass or less. Further, it is preferable that the mixing ratio of the oxime ester compound (C1) in the case of forming a thicker cured film is higher than the mixing ratio of the oxime ester compound (C1) in the case of forming a thinned cured film The oxime ester compound (C1) is formulated in the photosensitive composition.

Specific examples of the photopolymerization initiator other than the oxime ester compound (C1) and the aminoalkyl phenone-based photopolymerization initiator (C2) which can be used as the photopolymerization initiator (C) include: -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- Methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylamine Methyl benzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino- 2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, methyl o-besylbenzoate, 2,4-diethyl-9-oxygen Thiopurine 2-chloro-9-oxopurine 2,4-Dimethyl-9-oxothione 1-chloro-4-propoxy-9-oxothiolane Thiopurine 2-chlorothiazide 2,4-diethylthiopurine 2-methylthionine 2-isopropylthiopurine , 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl fluorene, azobisisobutyronitrile, benzammonium peroxide, hydroperoxide Propylbenzene, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(ortho Chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxy) Phenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimerization , benzophenone, 2-chlorobenzophenone, 4,4'-bis(dimethylamino)benzophenone (ie, miconesone), 4,4'-bis(diethylamino) Benzophenone (ie ethyl acesulfame), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone , p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pair Butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxybenzene Ethyl ketone, 9-oxopurine 2-methyl-9-oxothiolane 2-isopropyl-9-oxoxime , dibenzocycloheptanone, amyl 4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) heptane, 1,5-bis-(9 - aridinoyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytrimethylene, 2,4,6-tris(trichloromethyl)-allotriazole, 2- Methyl-4,6-bis(trichloromethyl)-homo-trimium, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) - each triterpenoid, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-allotriazole, 2-[2-(4-diethylamino)- 2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-allotriazole, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4, 6-bis(trichloromethyl)-homo-trimium, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-homo-trimium, 2-(4-ethoxyl Styryl)-4,6-bis(trichloromethyl)-homo-trimium, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-allotriazole, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4 -Methoxy)phenyl--tris-trimium, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl---tris-, 2,4- Bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl- All three, etc. These photopolymerization initiators may be used alone or in combination of two or more with the oxime ester compound (C1).

The photosensitive composition preferably contains an oxime ester compound (C3) together with the oxime ester compound (C1).
The oxime ester compound (C3) is a compound represented by the following formula (c3):
[化45]

(In the formula (c3), CR is a group represented by the following formula (c3a) or the following formula (c3b):
[Chem. 46]
,
R ^c1 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c2 and R ^c3 are each a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, and a cyclic organic group which may have a substituent 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, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, Or an aryl group which may have a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1).
As the CR in the formula (c3), the ease of synthesis or acquisition of the oxime ester compound represented by the formula (c3) or the ease of adjusting the characteristics of the oxime ester compound by the selection of R ^c2 and R ^c3 Preferably, it is a group represented by the formula (c3a).

In the group represented by the formula (c3a) or the formula (c3b) of CR in the formula (c3), R ^c1 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c1 is bonded to a 6-membered aromatic ring different from the aromatic ring to which the group represented by -(CO) _n2 - is bonded, on the condensed ring of formula (c3a) or formula (c3b). In the formula (c3a) or the formula (c3b), the bonding position of R ^c1 is not particularly limited. When the compound represented by the formula (c3) has one or more R ^c1 , it is preferable that one of the R ^c1 is one or more in terms of the synthesis of the compound represented by the formula (c3). The bond is bonded to the position shown by * in the structure represented by the following formula (c3a-1) and formula (c3b-1):
[化47]
.
In the case where R ^c1 is plural, the plurality of R ^c1 may be the same or different.

In the case where R ^c1 is an organic group, R ^c1 is not particularly limited insofar as it does not impair the object of the present invention, and may be appropriately selected from various organic groups. Preferable examples of the case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, a saturated aliphatic decyloxy group, and an alkoxycarbonyl group. a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyl methoxy group which may have a substituent, a phenylalkyl group having a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, may have a substituent Naphthylmethoxycarbonyl, naphthylalkyl group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl group which may have a substituent, amine group substituted by one or two organic groups, hydrazine Andolin-1-yl and piperidin-1-yl and the like.

When R ^c1 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R ^c1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, and n-pentyl group. Base, isopentyl, second pentyl, third amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-decyl, isodecyl, positive Sulfhydryl and isomeric groups. Further, when R ^c1 is an alkyl group, the alkyl group may have an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxy group. Ethoxyethyl and methoxypropyl and the like.

When R ^c1 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R ^c1 is an alkoxy group, the alkoxy group may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, trioctyloxy, n-decyloxy, isodecyloxy, n-decyloxy and isodecyloxy. Further, when R ^c1 is an alkoxy group, the alkoxy group may have an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Base, propoxyethoxyethoxy and methoxypropoxy groups, and the like.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of the case where R ^c1 is 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 the case where R ^c1 is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c1 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms of the saturated aliphatic fluorenyl group or the saturated aliphatic fluorenyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more. And 7 or less. Specific examples of the case where R ^c1 is a saturated aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, a n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, a n-pentamethylene group, and a 2,2-dimethyl group. Propyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-decyl fluorenyl group, n-dodecyl fluorenyl group, n-tridecyl fluorenyl group, positive fourteen Carbon sulfhydryl, n-pentadecacarbonyl and n-hexadecanthyl. Specific examples of the case where R ^c1 is a saturated aliphatic decyloxy group include an ethoxycarbonyl group, a propenyloxy group, a n-butenyloxy group, a 2-methylpropenyloxy group, and a n-pentamethyleneoxy group. , 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy, N-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy and n-hexadecyloxy.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of the case where R ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, and an isobutoxy group. Carbonyl, second butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, second pentyloxycarbonyl, third pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy Carbocarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, n-decyloxycarbonyl and isodecyloxy Alkylcarbonyl and the like.

When R ^c1 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Further, when R ^c1 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl group). ) Ethyl. In the case where R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl or naphthyl group.

In the case where R ^c1 is a heterocyclic group, the heterocyclic group is a monocyclic ring containing 5 or more members of N, S or O, or the monocyclic ring or the monocyclic ring is condensed with the benzene ring. A heterocyclic group. In the case where the heterocyclic group is a condensed ring, the number of rings constituting the condensed ring is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridinium, pyrimidine, and the like. Bismuth, benzofuran, benzothiophene, anthracene, isoindole, anthracene Benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quinazoline, indole, porphyrin, quinoxaline, piperidine, piperidine , porphyrin, piperidine, tetrahydropyran and tetrahydrofuran. In the case where R ^c1 is a heterocyclic group, the heterocyclic group may further have a substituent.

In the case where R ^c1 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where R ^c1 is a heterocyclic group.

In the case where R ^c1 is an amine group substituted with one or two organic groups, examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, and a carbon number of 3 or more and 10 or less. a cycloalkyl group, a saturated aliphatic fluorenyl group having 2 or more and 21 or less carbon atoms, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, and a carbon atom having a substituent of 7 or more and 20 or less A phenylalkyl group, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such preferred organic groups are the same as R ^c1 . Specific examples of the amine group substituted with one or two organic groups include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamine group, and a n-butylamino group. , di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-nonylamino, anilino, naphthylamino, acetaminophen, propionium Amino, n-butylammonium, n-pentamethylene, n-hexylamine, n-heptylamino, n-octylamine, n-nonylamine, benzamidine, alpha-naphthylamine Base and β-naphthylamino group and the like.

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in the R ^c1 further have a substituent include an alkyl group having 1 or more and 6 or less carbon atoms, and a carbon number of 1 or more and 6 or less. Alkoxy group, a saturated aliphatic fluorenyl group having 2 or more and 7 or less carbon atoms, an alkoxycarbonyl group having 2 or more and 7 or less carbon atoms, a saturated aliphatic decyloxy group having 2 or more and 7 or less carbon atoms, a monoalkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a dialkylamino group having an alkyl group having 1 or more and 6 or less, porphyrin-1-yl, and piperidin-1- Base, halogen, nitro and cyano groups. In the case where the phenyl group, the naphthyl group and the heterocyclic group contained in R ^c1 further have a substituent, the number of the substituents is not limited insofar as it does not impair the object of the present invention, and is preferably 1 or more and 4 the following. When the phenyl group, the naphthyl group and the heterocyclic group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the above-mentioned examples, R ^c1 is a group represented by a nitro group or R ^c6 -CO-, and the sensitivity tends to be improved, which is preferable. R ^c6 is not particularly limited insofar as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of the preferred group of R ^c6 include an alkyl group having 1 or more and 20 or less carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. . As R ^c6 , among these groups, 2-methylphenyl, thiophen-2-yl and α-naphthyl are particularly preferable.

In the formula (c3a), R ^c2 and R ^c3 are each a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c2 and R ^c3 may be bonded to each other to form a ring. Among these groups, R ^c2 and R ^{c3 are} preferably a chain alkyl group which may have a substituent. In the case where R ^c2 and R ^c3 are a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ^c2 and R ^c3 are a chain alkyl group having no substituent, the number of carbon atoms of 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 Above and below 6. Specific examples of the case where R ^c2 and R ^c3 are a chain alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, and third group. Butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-decyl, Isoindolyl, n-decyl and isodecyl. Further, when R ^c2 and R ^c3 are an alkyl group, the alkyl group may have an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxy group. Ethoxyethyl and methoxypropyl and the like.

When R ^c2 and R ^c3 are a chain-like alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more. And 6 or less. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The alkyl group may have a substitution without particular limitation insofar as it does not impair the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the cycloalkyl group are the same as those in the case where R ^c1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. Specific examples of the heterocyclic group are the same as those in the case where R ^c1 is a heterocyclic group. When R ^c1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

In the case where the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of the 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 a chain alkoxy group having no substituent, the number of carbon atoms of the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably It is 1 or more and 6 or less. Specific examples of the case where R ^c2 and R ^c3 are a chain alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and an isobutoxy group. Second butoxy, n-butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyl An oxy group, a second octyloxy group, a third octyloxy group, a n-decyloxy group, an isodecyloxy group, a n-decyloxy group, an isodecyloxy group or the like. Further, when R ^c2 and R ^c3 are alkoxy groups, the alkoxy group may have an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Base, propoxyethoxyethoxy and methoxypropoxy groups, and the like.
In the case where R ^c2 and R ^c3 are a chain alkoxy group having a substituent, the alkoxy group may have the same substituent as in the case where R ^c2 and R ^c3 are a chain alkyl group.

When R ^c2 and R ^c3 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. In the case where R ^c2 and R ^c3 are a cyclic organic group, the cyclic organic group may have the same substituent as in the case where R ^c2 and R ^c3 are a chain alkyl group.

When R ^c2 and R ^c3 are an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group in which a plurality of benzene rings are bonded via a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed. In the case where the aromatic hydrocarbon group is a group in which a phenyl group or a plurality of benzene rings are bonded or condensed, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, especially preferably 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.

In the case where R ^c2 and R ^c3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isodecyl, tricyclodecyl, Tricyclic fluorenyl, tetracyclododecyl and adamantyl.

In the case where R ^c2 and R ^c3 are heterocyclic groups, the heterocyclic group is a single ring of 5 or 6 members containing 1 or more of N, S or O, or the monocyclic ring or the monocyclic ring and benzene. A heterocyclic group formed by condensation of a ring. In the case where the heterocyclic group is a condensed ring, the number of rings constituting the condensed ring is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridinium, pyrimidine, and the like. Bismuth, benzofuran, benzothiophene, anthracene, isoindole, anthracene Benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quinazoline, indole, porphyrin, quinoxaline, piperidine, piperidine , porphyrin, piperidine, tetrahydropyran and tetrahydrofuran.

R ^c2 and R ^c3 may be bonded to each other to form a ring. The group comprising a ring formed by R ^c2 and R ^{c3 is} preferably a cycloalkylene group. In the case where R ^c2 and R ^{c3 are} bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

In the case where the group formed by the bonding of R ^c2 and R ^c3 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring condensable with the cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a furan ring. A thiophene ring, a pyrrole ring, a pyridine ring, a pyridinium ring, and a pyrimidine ring.

Examples of the preferred groups of R ^c2 and R ^c3 described above include the groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group. A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkyl group of A ¹ is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. In the case where A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferred, and a fluorine atom, a chlorine atom or a bromine atom is more preferred. In the case where A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. In the case where A ² is a cyclic organic group, the cyclic organic group is the same as the cyclic organic group which R ^c2 and R ^{c3 have} as a substituent. In the case where A ² is an alkoxycarbonyl group, the alkoxycarbonyl group is the same as the alkoxycarbonyl group which R ^c2 and R ^{c3 have} as a substituent.

Preferred examples of R ^c2 and R ^c3 include an alkyl group such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl and n-octyl; 2-methoxyethyl, 3- Methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl , 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy Alkoxyalkyl group such as heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6 a cyanoalkyl group such as cyano n-hexyl, 7-cyano-n-heptyl or 8-cyano-n-octyl; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, Phenylalkyl such as 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl and 8-phenyl-n-octyl; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl , 4-cyclohexyl n-butyl, 5-cyclohexyl n-pentyl, 6-cyclohexyl n-hexyl, 7-cyclohexyl n-heptyl, 8-cyclohexyl n-octyl, 2-cyclopentylethyl, 3- Cyclopentyl n-propyl, 4-cyclopentyl n-butyl, 5-cyclopentyl a cycloalkylalkyl group such as n-pentyl, 6-cyclopentyl n-hexyl, 7-cyclopentyl n-heptyl and 8-cyclopentyl n-octyl; 2-methoxycarbonylethyl, 3-methoxy Carbonyl n-propyl, 4-methoxycarbonyl n-butyl, 5-methoxycarbonyl n-pentyl, 6-methoxycarbonyl n-hexyl, 7-methoxycarbonyl n-heptyl, 8-methoxycarbonyl n-Octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexane Alkoxycarbonylalkyl such as 7-ethoxycarbonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5 -chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-positive Pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro A halogenated alkyl group such as n-pentyl.

As R ^c2 and R ^c3 , preferred ones of the above are: ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl , 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl and 3,3,4,4,5, 5,5-heptafluoro-n-pentyl.

Examples of preferred organic groups for R ^c4 include, in the same manner as R ^c1 : an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, or a saturated aliphatic group. a decyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzamidine which may have a substituent a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, A naphthylmethoxycarbonyl group having a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine substituted with one or two organic groups Base, porphyrin-1-yl and piperidin-1-yl and the like. Specific examples of such groups are the same as those described for R ^c1 . Further, as R ^c4 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The phenoxyalkyl group and the phenylthioalkyl group may have the same substituent as the substituent which the phenyl group contained in R ^c1 may have.

Among the organic groups, R ^{c4 is} preferably an alkyl group, a cycloalkyl group, a phenyl group or a cycloalkylalkyl group which may have a substituent, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, and still more preferably an alkyl group having 1 or more and 4 or less carbon atoms. Good for methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of 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 still more preferably 5 or 6. The number of carbon atoms of 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 of the alkylene group contained in the phenylthioalkyl group having 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 still more preferably 2 or less. Among the phenylthioalkyl groups having a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferred.

Further, the group represented by R ^c4 and -A ³ -CO-OA ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

In the case where A ³ is an alkylene group, the alkyl group may be linear or branched, preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and still more preferably 1 or more and 4 or less.

Preferable examples of A ⁴ include an alkyl group having 1 or more and 10 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and a cycloalkylalkyl group having 4 or more and 10 or less carbon atoms. An aralkyl group having 7 or more and 20 or less carbon atoms, and an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms. Preferred examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-pentyl group and n-hexyl group. Phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl and β-naphthylmethyl.

Preferred examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-Butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methyl Oxycarbonylcarbonyl n-propyl, 3-ethoxycarbonyl n-propyl, 3-n-propoxycarbonyl n-propyl, 3-n-butoxycarbonyl n-propyl, 3-n-pentyloxycarbonyl n-propyl, 3-n-hexyloxycarbonyl n-propyl, 3-benzyloxycarbonyl-n-propyl, 3-phenoxycarbonyl-n-propyl and the like.

As described above, R ^c4 is preferred, and R ^{c4 is} preferably a group represented by the following formula (c3-a) or (c3-b).
[48]

(In the formulae (c3-a) and (c3-b), R ^c7 and R ^c8 are each an organic group, and n3 is an integer of 0 or more and 4 or less, and R ^c7 and R ^c8 are present in an adjacent position on the benzene ring. In this case, R ^c7 and R ^c8 may be bonded to each other to form a ring, n4 is an integer of 1 or more and 8 or less, n5 is an integer of 1 or more and 5 or less, and n6 is an integer of 0 or more and (n5+3) or less, R ^c9 Organic base)

Examples of the organic group of R ^c7 and R ^{c8 in} the formula (c3-a) are the same as those of R ^c1 . As R ^c7 , an alkyl group or a phenyl group is preferred. When R ^c7 is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 3 or less, and most preferably 1. That is, R ^{c7 is} most preferably a methyl group. In the case where R ^c7 and R ^{c8 are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (c3-a) and in which R ^c7 and R ^c8 form a ring include naphthyl-1-yl or 1,2,3,4-tetrahydronaphthalen-5-yl. . In the above formula (c3-a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In the above formula (c3-b), R ^c9 is an organic group. The organic group may be the same as the organic group described for R ^c1 . Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 3 or less. As R ^c9 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or the like is preferably exemplified, and among these, a methyl group is more preferable.

In the above formula (c3-b), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, more preferably 1 or 2. In the above formula (c3-b), n6 is 0 or more and (n5+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (c3-b), n4 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 the formula (c3), R ^c5 is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent. The substituent which may be contained in the case where R ^c5 is an aliphatic hydrocarbon group is preferably a phenyl group, a naphthyl group or the like. In addition, a substituent which may be contained in the case where R ^c1 is an aryl group, and an alkyl group, an alkoxy group, a halogen atom or the like having 1 or more and 5 or less carbon atoms is preferably exemplified.

In the formula (c3), as R ^c5 , a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-cyclopentylethyl group or a 2-cyclobutyl group can be preferably exemplified. A group, a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group or the like, among these, a methyl group or a phenyl group is more preferable.

Preferred examples of the compound represented by the formula (c3) include the following compounds.
[化49]

[化50]

[化51]

[化52]

[化53]

The content of the photopolymerization initiator (C) in the photosensitive composition is not particularly limited insofar as it does not impair the object of the present invention. The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.3% by mass or more and 30% by mass or less, based on the mass of the solid content component of the photosensitive composition. It is preferably 0.5% by mass or more and 20% by mass or less. By using the photopolymerization initiator (C) in an amount within the range, it is easy to obtain a photopolymerization initiator by using a photopolymerization initiator without impairing the mechanical properties, solvent resistance, chemical resistance, and the like of the cured product ( C) the desired effect.

<Sunscreen (D)>
The photosensitive composition contains an opacifier (D). The sunscreen (D) must contain a resin-coated carbon black (D1). Therefore, by using a photosensitive composition, it is easy to obtain a cured film excellent in both light-shielding property and insulating property.

The uncoated carbon black which is not coated with the resin as the object to be coated with the resin is not particularly limited, and various carbon blacks which have been conventionally used as an opacifier can be used. As the uncoated carbon black, a known carbon black such as chimney black, furnace black, hot carbon black, or lamp black can be used.
The uncoated carbon black may be used alone or in combination of two or more.

As the uncoated carbon black, carbon black which is subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into the carbon black shows an acidic functional group based on the definition of Bronsted acid. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The introduction of an acidic group of carbon black forms a salt. The cation which forms a salt with an acidic group is not specifically limited in the range which does not impair the objective of this invention. Examples of the cation include various metal ions, a cation of a nitrogen-containing compound, an ammonium ion, and the like, and an alkali metal ion such as a sodium ion, a potassium ion or a lithium ion or an ammonium ion is preferable.

In the carbon black to which the acidic group is introduced, the light-shielding cured film formed by using the photosensitive composition achieves high electrical resistance, and preferably has a carboxylic acid group or a carboxylic acid. a carbon black of one or more functional groups of a group consisting of a salt group, a sulfonic acid group, and a sulfonate group.

The method of introducing an acidic group into carbon black is not particularly limited. As a method of introducing an acidic group, the following methods are mentioned, for example.
1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or the like or an indirect substitution method using sulfite or bisulfite.
2) A method of diazo coupling an organic compound having an amine group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with a carbon black having a hydroxyl group by an etherification method of Williamson (Williamson).
4) A method of reacting an organic compound having a halogenated carbonyl group with an acidic group protected by a protective group with a carbon black having a hydroxyl group.
5) A method of deprotecting a carbon black by a Friedel-Crafts reaction using an organic compound having a halogenated carbonyl group and an acidic group protected by a protective group.

Among these methods, the method 2) is preferable in terms of the ease of introduction of the acidic group and the safety. The organic compound having an amine group and an acidic group used in the method 2) is preferably a compound having an amine group and an acidic group bonded to an aromatic group. As an example of such a compound, an aminobenzoic acid such as an aminobenzenesulfonic acid or a 4-aminobenzoic acid such as an aminobenzenesulfonic acid may be mentioned.

The number of moles of the acidic group introduced into the carbon black is not particularly limited insofar as it does not impair the object of the present invention. The number of moles of the acidic group introduced into the carbon black is preferably 1 mmol or more and 200 mmol or less, more preferably 5 mmol or more and 100 mmol or less with respect to 100 g of carbon black.

The method of coating the uncoated carbon black with a resin is not particularly limited.
As a coating method, a method of removing a solvent from a coating layer after coating a particle of carbon black with a solution of a resin, a dispersion containing fine particles of a resin, or an emulsion is exemplified.
Further, when the resin is coated with a curable resin, the monomer or the uncured resin precursor may be adhered to the surface of the carbon black particles, and then the monomer may be polymerized or the uncured resin precursor may be cured. In this case, it is preferred to coat the particles of the carbon black by using a solution of the monomer or the uncured resin precursor to adhere the monomer or the uncured resin precursor to the surface of the carbon black particles. Further, a polymerization initiator or a hardener may be used together with a monomer or an uncured resin precursor as needed.

After the carbon black particles are dispersed in a matrix containing a resin, the resin containing the carbon black particles is finely pulverized to produce a resin-coated carbon black resin (D1).

The thickness of the resin coating layer in the resin-coated carbon black (D1) is preferably 0.5 nm or more and 50 nm or less.

The resistivity of the resin-coated carbon black (D1) as a dry powder, that is, the powder resistance is preferably 0.5 Ω·cm or more and 50 Ω·cm or less.
When a photosensitive composition containing such a resin-coated carbon black (D1) is used, it is easy to form a cured film having a high volume resistivity and excellent adhesion to a substrate and light-shielding properties.

Examples of the resin which can be used for the coating of carbon black include thermosetting such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, kansui resin, epoxy resin, and alkylbenzene resin. Resin, or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyfluorene, polyparaphenylene terephthalamide A thermoplastic resin such as polyamidoximine, polyimine, polyamine-based bismaleimide, polyether sulfopolyphenylene fluorene, polyarylate, polyetheretherketone or the like. Among them, an epoxy resin can be preferably used.

The form of the light-shielding agent (D) such as the resin-coated carbon black (D1) used for the preparation of the photosensitive composition is not particularly limited. The sunscreen (D) can be used as a powder or as a dispersion. The opacifier (D) is preferably used as a dispersion for the preparation of a photosensitive composition.
As the dispersion, a dispersion containing two or more kinds of light-shielding agents can be used. Further, two or more kinds of dispersion liquids each containing a different type of light-shielding agent can be used.

The light-shielding agent (D) containing the resin-coated carbon black (D1) is preferably used as a dispersion liquid dispersed in a dispersion medium as described above. As the dispersion medium, for example, propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, and propionic acid 3- can be used. An organic solvent such as ethoxyethyl ester or propylene glycol monomethyl ether propionate or water.

In order to stabilize the dispersion of the opacifier (D) in the dispersion or to improve the dispersibility of the opacifier (D) in the photosensitive composition, a dispersant may be added to the opacifier (D).
As the dispersing agent, a poly(ethylenimine)-based, urethane-based resin-based or acrylic-based polymer-dispersing agent is preferably used. Since the opacifier (D) contains a resin-coated carbon black (D1), it is preferable to use a dispersion of an acrylic resin-based dispersant or a urethane resin which can be suitably used for dispersion of carbon black as a dispersing agent. Agent.
Further, there is also a case where a corrosive gas due to a dispersing agent is generated from the cured film. Therefore, the sunscreen (D) is preferably a dispersion treatment without using a dispersant.

The viscosity of the dispersion is not particularly limited. The viscosity of the dispersion is preferably 3 mPa·s or more and 200 mPa·s or less as a value measured at 25 ° C by a cone-plate type viscometer. The blending ratio of the resin-coated carbon black to the dispersion medium is not limited as long as it is the viscosity in the range, and varies depending on the type of the dispersion medium. As an example, the resin-coated carbon black content is dispersed by containing the resin-coated carbon black. 1% by mass or more and 50% by mass or less of the entire liquid.

The particle diameter of the opacifier (D) in the dispersion is preferably 80 nm or more and 300 nm or less in terms of the dispersed average particle diameter. The dispersed average particle size can be measured using a laser diffraction type particle size distribution system.

When the photosensitive composition contains the resin-coated carbon black (D1) as the light-shielding agent (D), the photosensitive composition can be used to form a cured film having a high volume resistivity. Therefore, the insulation of the cured film caused by the increase in carbon black is prevented from being significantly lowered, and the cured film having a high unit optical density is easily formed.

On the other hand, when a photosensitive film having a high unit optical density is formed by using a photosensitive composition, when the coating film containing the photosensitive composition is exposed, the hardening of the deep portion of the coating film is likely to be insufficient. . However, when the photosensitive composition contains the above-described oxime ester compound (C1) as a photopolymerization initiator (C), it is easy to sufficiently harden the deep portion of the coating film, and it is easy to form a cured film having good adhesion to the substrate. At the same time, the cross section of the black matrix pattern containing the cured composition of the photosensitive composition is a forward cone, and when the liquid crystal display panel or the liquid crystal display device is formed using the cured product of the photosensitive composition, the opacity of the end face of the pattern can be reduced ( Detailed below).
Further, if the deep portion of the coating film is sufficiently cured, the durability of the cured film in a high-temperature, high-humidity, high-pressure environment is improved, and even if the cured film is exposed to such a harsh environment, it is difficult for water to be immersed into the interior of the cured film, and The adhesion of the cured film to the substrate or the volume resistivity (higher insulation) is also not easily impaired.

Further, with the realization of a higher unit optical density, it is easy to make the thickness of the black matrix containing the cured product of the photosensitive composition thin. If a thin black matrix is used, the glazing of the pattern end faces of the black matrix in the liquid crystal display device can be further reduced, and the material cost can be reduced.

The photosensitive composition may contain, as a light shielding agent (D), a light-shielding agent other than the resin-coated carbon black (D1) together with the resin-coated carbon black (D1). When the photosensitive composition contains another light-shielding agent, the ratio of the mass of the resin-coated carbon black (D1) in the mass of the light-shielding agent (D) is preferably 50% by mass or more, more preferably 70% by mass or more, and further It is preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more.

Examples of other light-shielding agents which can be used together with the resin-coated carbon black include carbon black, an internal phthalamide pigment, fine particles containing silver tin (AgSn) alloy as a main component, titanium black, copper, iron, manganese, and the like. Any of various organic and inorganic pigments such as metal oxides, composite oxides, metal sulfides, metal sulfates, or metal carbonates such as cobalt, chromium, nickel, zinc, calcium, and silver.

In the photosensitive composition, a pigment such as a resin-coated carbon black (D1) and a dye may be used in combination as the light-shielding agent (D). The dye can be appropriately selected from known materials.
Examples of the dye which can be applied to the photosensitive composition include an azo dye, a metal salt azo dye, an anthraquinone dye, a triphenylmethane dye, a dibenzopyran dye, a cyanine dye, and a naphthoquinone dye. , quinone imine dye, methine dye, phthalocyanine dye, and the like.
Further, these dyes can be dispersed in an organic solvent or the like by lake formation (salting), and used as an opacifier (D).
In addition to the above-mentioned dyes, for example, Japanese Patent Laid-Open Publication No. 2013-225132, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A dye or the like described in Japanese Laid-Open Patent Publication No. 2014-197206, and the like.

The total amount of the content of the opacifier (D) in the photosensitive composition can be appropriately selected within the range not impairing the object of the present invention, and is preferably 90 in terms of the mass of the solid content of the resin composition as a whole. The mass% or less is preferably 2% by mass or more and 85% by mass or less, more preferably 3% by mass or more and 80% by mass or less. Further, as long as a photosensitive composition can be used to form a cured film having a sufficiently high light-shielding property, the total amount of the total amount of the light-shielding agent (D) can be 90% or more with respect to the mass of the solid content of the photosensitive composition as a whole. The mass% or less may be 85% by mass or less, or may be 80% by mass or less.
Further, in the present specification, the amount of the above-mentioned light-shielding agent (D) may be defined as a value which also contains the amount of the dispersing agent which is present together with the light-shielding agent (D).

<Other ingredients (E)>
Hereinafter, any component which is another component will be described. The amount of addition of the other component (E) is not particularly limited. Other components (E) in an amount that does not impair the purpose of the object of the present invention can be used.

(surface conditioner)
The surface conditioner suppresses the appearance defect (non-uniform distribution of the pigment) caused by surface defects or uneven distribution of the pigment by lowering the surface tension of the photosensitive composition. Specifically, polydimethyl methoxy olefin, polyether modified polyoxy siloxane, polymethyl alkyl decane, poly fluorene modified by aralkyl or polyester chain can be preferably used. Oxytomane, etc.

(adhesion enhancer)
A known coupling agent such as a decane coupling agent, a titanate coupling agent, or an aluminate coupling agent can be used. Among them, a decane coupling agent can be preferably used from the viewpoint of improving the adhesion to the glass substrate.

The photosensitive composition may contain various additives other than the above as needed. Specific examples thereof include a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a filler, an antioxidant, an ultraviolet absorber, an anti-aggregating agent, a thermal polymerization inhibitor, an antifoaming agent, and an interfacial activity. Agent, chain transfer agent, photoinitiator, solvent, and the like. Regarding any of the additives, previously known additives can be used.

Examples of the surfactant include an anionic compound, a cationic compound, and a nonionic compound.
Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether.
Examples of the antifoaming agent include a polyfluorene-based compound and a fluorine-based compound.
Examples of the chain transfer agent include a thiol compound, a halogen compound, an anthraquinone compound, and an α-methylstyrene dimer. By including a chain transfer agent, the pattern shape (especially the CD (critical dimension) change, the exposure margin) of the hole pattern can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) can also reduce sublimation or coloration and odor in addition to the above effects. Better words.
Examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-di Isoamyl methylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4' - bis(dimethylamino)benzophenone (commonly known as micbutone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-B Base-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene. These photoinitiating aids may be used alone or in combination of two or more.

<Solvent (S)>
The photosensitive composition preferably contains a solvent (S) for dilution. Examples of the solvent (S) 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 single. 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 monoethyl ether, etc. Monoalkyl ethers; 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) alkyl glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, Other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; milks such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyl esters; ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, propionic acid 3 -methyl-3-methoxybutyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate Ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate Other esters such as ethyl ester and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-II A guanamine such as methyl acetamide. These solvents may be used singly 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 (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether (MEDG), cyclohexanone, and 3-methoxybutyl acetate (MBA) exhibit excellent solubility to the above photopolymerization initiator (C), and thus it is preferred to use propylene glycol monomethyl ether. Acetate, 3-methoxybutyl acetate.
The content of the solvent (S) is preferably such that the solid content concentration of the photosensitive composition is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 40% by mass or less.

制备Preparation method of photosensitive composition≫
In the photosensitive composition, the above components are uniformly stirred and mixed, and uniformly dissolved and dispersed to prepare. When mixing, it can be mixed using a mixer such as a roll mill, a ball mill, or a sand mill. It can be prepared by filtration using a filter such as a 2 μm membrane filter as needed.

Method for forming hardened material and hardened material
The method of forming a cured product is the same as the method of forming a prior art using a photosensitive composition, except that the above photosensitive composition is used.

The method of forming the cured product using the above photosensitive composition is not particularly limited and may be appropriately selected from the methods previously employed. The cured product is formed into a molded body having a desired shape by the control of the shape of the coating film at the time of application of the photosensitive composition or the combination of positional selective exposure and development. A preferred method for forming a cured product includes a coating film forming step of forming a coating film using the photosensitive composition, and a method of exposing the coating film to an exposure step. In the case where the exposure is selectively performed at a position, the exposed coating film can be developed by a developing solution to obtain a patterned cured product.

First, in the coating film forming step, for example, a contact transfer type coating device, a rotator (rotary coating device), or a shower curtain type using a roll coater, a reverse coater, a bar coater or the like is used. A non-contact type coating apparatus such as a curtain flow coater applies the photosensitive composition onto a substrate on which a cured product is to be formed, and if necessary, removes a solvent by drying (prebaking) to form a coating film.
Further, the photosensitive composition for depositing a droplet on a substrate or a concave portion in which a substrate having irregularities is embedded, or a photosensitive composition filled in a concave portion of a mold is also referred to as a "coating film" for convenience. "."

The film thickness of the cured photosensitive composition formed by using the photosensitive composition and the layer thickness of the light shielding layer (black matrix) are not particularly limited, but are preferably 0.2 μm or more, and more preferably 0.3 μm or more and 5 μm. Hereinafter, it is more preferably 0.4 μm or more and 3 μm or less, and most preferably 0.5 μm or more and 2 μm or less.

Then, the formed coating film is supplied to the exposure step. In the exposure step, the coating film is irradiated with ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, The coating film is exposed by radiation or electromagnetic waves such as i-rays, g-rays, and h-rays. Exposure to the coating film can be carried out in a positionally selective manner via a negative mask. The amount of exposure varies depending on the composition of the photosensitive composition, and is preferably, for example, about 10 mJ/cm ² or more and 600 mJ/cm ² or less.

The exposed coating film is developed as needed.
The photosensitive composition is less likely to be excessively dissolved in the alkaline developing solution after exposure. Therefore, by using the photosensitive composition described above, it is easy to form a patterned cured product having an exposed portion as a convex portion and an unexposed portion as a concave portion.

In the developing step, the exposed coating film is developed by using a developing solution to form a cured product patterned into a desired shape. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developer include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt.

Further, post-baking of the cured product after exposure or the developed patterned cured product may be carried out as needed to further promote heat hardening. The post-baking temperature is preferably 150 ° C or more and 270 ° C or less.

The cured product is formed using the above photosensitive composition. The use of the cured product is not particularly limited. The cured product can be preferably used as a black matrix used in various color filters for image display devices. A color filter having a black matrix including a cured product formed using the above photosensitive composition can be preferably used for an image display panel. The image display panel can be preferably used in various image display devices such as a liquid crystal display device, an organic EL (Electroluminescence) display device, and an inorganic EL display device. Further, similarly, it can be preferably used in a touch panel having both an image display panel and a surface sensor including a capacitance electrode or a resistance electrode.

≪Color filter and image display panel≫
Hereinafter, an example of the image display panel 1 including the color filter 100 will be described with reference to FIG.
FIG. 3 is a view schematically showing a cross section of the liquid crystal display panel 1 that displays an image as a representative example of the image display panel 1.
In the image display panel 1, a polarizing layer 50b, a TFT (thin film transistor) supporting substrate 90b, a liquid crystal layer 30, a color filter 100, a CF (color filter) supporting substrate 90a, and a polarizing layer 50a are sequentially laminated.
In the liquid crystal layer 30, spacers having a layer thickness of the liquid crystal layer 30 having a constant thickness are provided at specific intervals in the in-plane direction (not shown).

The polarizing layer 50a and the polarizing layer 50b are disposed to form a specific polarization angle. Further, a backlight device (not shown) is provided on the side of the image display panel 1 on which the polarizing layer 50b is provided.
Each of the CF supporting board 90a and the TFT supporting board 90b includes a light transmissive material such as glass or a transparent resin for transmitting light emitted from the backlight.

The color filter 100 is provided on the liquid crystal layer 30 side of the CF support substrate 90a by the CF support substrate 90a. The color filter 100 includes a light shielding layer 10 and colored layers 20a, 20b, and 20c. The light shielding layer 10 corresponds to a black matrix.
Further, the hue of the colored layers 20a, 20b, and 20c is not black, and typically red (R), green (G), blue (B), and the like are colored.
The colored layers 20a, 20b, and 20c are the first colored layer 20a, the second colored layer 20b, and the third colored layer 20c through which light of different hue is transmitted. The hue of the first colored layer 20a, the second color filter 20b, and the third 20c are, for example, red (R), green (G), and blue (B).
The wiring 40 is formed on the surface of the TFT supporting substrate 90b on the liquid crystal layer 30 side. As the TFT supporting substrate 90b, a known TFT substrate can be used.

The light shielding layer 10 contains a cured product of the above photosensitive composition. Therefore, the light shielding layer 10 exhibits a desired higher unit optical density. Further, the cross-sectional shape of the light shielding layer 10 is as shown in FIG. 1 below, and is a forward cone with respect to the support substrate 90a.
[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples.

[Examples 1 to 3 and Comparative Examples 1 to 5]
Alkali-soluble resin (A-1), photopolymerizable monomer (B-1), photopolymerization initiator (C-1, C-2, C-3, and C-4), and sunscreen (D-1) And D-2) and the additives (E-1 and E-2) are dispersed and dissolved in an organic solvent (including a mixed solvent of S-1, S-2, and S-3) in the ratios shown in Table 1, respectively. A photosensitive composition was prepared. The mixing ratio of each of the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, the light-shieling agent, and the additive as a solid component is as shown in Table 1 in terms of parts by mass. Further, the organic solvent was prepared so that the concentration of the solid content component in the photosensitive composition was 15% by mass.

[Table 1]

Among them, the alkali-soluble resin (A) is used by preparing a Cardo resin. The preparation method of Cardo resin is shown in Preparation Example 1.

[Preparation Example 1]
Add bisphenol hydrazine type epoxy resin (epoxy equivalent 235) 235 g, tetramethylammonium chloride 110 mg, 2,6-di-tert-butyl-4-methylphenol 100 to a 500 mL four-necked flask. Mg and 72.0 g of acrylic acid were dissolved while being blown into the air at a rate of 25 mL/min., and heated to 90 ° C or higher and 100 ° C or lower. Next, the solution was slowly heated while the solution was cloudy, and heated to 120 ° C to be completely dissolved. At this time, the solution gradually became transparent and viscous, and stirring was continued in this state. During this period, the acid value was measured and stirring was continued until it became less than 1.0 mgKOH/g. It takes 12 hours for the acid value to become the target value. Then, it was cooled to room temperature to obtain a bisphenolphthalein type epoxy acrylate represented by the following formula which was colorless, transparent and solid.

[54]

Then, after dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of the above-mentioned bisphenolphthalein type epoxy acrylate, 80.5 g of benzophenone tetracarboxylic dianhydride and tetraethyl bromide were mixed. 1 g of ammonium chloride was slowly heated to 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin (R-1) as a Cardo resin. The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

As the photopolymerizable monomer (B), a photopolymerizable monomer M-1 (DPHA (manufactured by Nippon Kayaku Co., Ltd.), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) is used.

As the photopolymerization initiator (C-1), the following P-1, P-2, P-3, and P-4 were used.
[化55]

Further, as the light-shielding agent (D), the light-shielding agent D-1 and the light-shielding agent D-2 which are dispersion liquids of the light-shielding agent were used, respectively.
The sunscreen D-1 is an epoxy resin coated carbon black dispersion (the dispersion medium is propylene glycol monomethyl ether acetate (PM)). Regarding the light-shielding agent D-1, the resin-coated carbon black had a dispersed average particle diameter of 130 nm and a powder resistance of 5 Ω·cm. Further, the light-shielding agent D-2 is a carbon black dispersion liquid which is not coated with a resin (the dispersion medium is propylene glycol monomethyl ether acetate (PM)). Regarding the sunscreen D-2, the dispersed average particle diameter of the carbon black was 110 nm, and the powder resistance was 1.0 × 10 ^-6 Ω·cm which is the lower limit of the measurement limit. In addition, in Table 1, the description of the weight parts of the light-shielding agents D-1 and D-2 is described based on the weight of each solid content component.

As the additive E-1, BYK-310 (manufactured by BYK-Chemie Japan Co., Ltd.) containing a polyester-modified polydimethylsiloxane as a surface conditioning agent was used. As the additive E-2, 3-phenylamino-n-propyl (trimethoxy)decane was used as the adhesion promoter.

As the solvent, the following S-1, S-2 and S-3 were mixed and used as a mixed solvent. The mixing ratio (weight ratio) was S-1:S-2:S-3=50:30:20.
S-1: 3-methoxybutyl acetate (MA)
S-2: propylene glycol monomethyl ether acetate (PM)
S-3: cyclohexanone (AN)
Here, S-2 contains the dispersion medium of the above-mentioned sunscreen agents D-1 and D-2.

Using the photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 5, the cured product of the photosensitive composition was evaluated in accordance with the following production method and measurement method.

<Production of substrate Cg having cured film>
The photosensitive composition obtained in each of the examples and the comparative examples was applied onto a glass substrate of 100 × 100 mm and 0.7 mm thick using a spin coater, and then the coating film was prebaked at 90 ° C for 60 seconds. Bake to obtain a cured film having a film thickness of 1.2 μm.
Then, using the exposure apparatus TME150RTO (manufactured by TOPCON), the coating film was subjected to full-surface exposure (exposure by ultraviolet light of an ultrahigh pressure mercury lamp) at an exposure amount of 40 mJ/cm ² without using a mask.
After the exposure, an aqueous solution of potassium hydroxide having a concentration of 0.05% by mass was used as a developing solution, and development was carried out at 25 ° C for 60 seconds.
The developed coating film was post-baked at 230 ° C for 30 + 180 minutes (total 210 minutes) to obtain a substrate Cg.

<Measurement of unit optical density>
With respect to the substrate Cg, the optical density of the cured film was measured using an optical density measuring device D-200II (manufactured by Gretag Macbeth), and the unit optical density (unit: /μm) was obtained by conversion of the film thickness. . The results are shown in Table 2.

<Measurement of adhesion>
A lattice-shaped slit (cross-cut) having a width of 1 mm was cut in the cured film in the substrate Cg.
Then, a PCT test (pressure cooker test) of 36 hours of exposure was carried out in an environment of 120 ° C, humidity of 100%, and 2 atmospheres.
Thereafter, the mixture was returned to room temperature, and subjected to a tape peeling test specified in ASTM-D3359-09e2, and the presence or absence of peeling of each of the lattices was observed. The results of the tape peeling test were evaluated based on the following criteria. The results are shown in Table 2.
◎ (Grade 5B): No peeling at all.
○ (Grade 4B): The ratio of the number of cured films peeled off to the total number of cured films divided by the lattice cut is 5% or less.
Δ (Grade 3B): The ratio of the number of cured films peeled off to the total number of cured films divided by lattice cutting is more than 5% and 15% or less. The peeling is more than 15%.
× (Grade 2B to 0B): The ratio of the number of cured films peeled off to the total number of cured films divided by lattice cutting is 15% or more.

<Production of substrate Cs having a cured film>
Instead of a glass substrate, a 5 inch low resistance 矽 wafer (surface resistance: 0.01 to 0.03 Ω) was used. The photosensitive composition obtained in each of the examples and the comparative examples was used to obtain a substrate Cs having a cured film of a photosensitive composition by the same production method as that of the substrate Cg.

<Measurement of volume resistance value>
For the substrate Cs, a PCT test of exposure for 1 hour was carried out in an environment of 120 ° C, humidity of 100%, and 2 atmospheres. Thereafter, the temperature was returned to room temperature, and the volume resistivity of the cured film was calculated by a method according to JIS-K6911 using a resistivity meter Hiresta MCP HT-450 (manufactured by Mitsubishi Chemical Corporation) (measurement conditions: voltage 10 V, 60 seconds) ). The results are shown in Table 2.
◎: 1.0 × 10 ¹⁴ Ω·cm or more.
○: 1.0 × 10 ¹³ to 9.9 × 10 ¹³ Ω·cm.
×: 9.9 × 10 ¹² Ω·cm or less.

<Production of Substrate Pg Having Patterned Cured Film>
The photosensitive composition obtained in each of the examples and the comparative examples was applied onto a glass substrate of 100 × 100 mm and 0.7 mm thick by a spin coater, and then the coating film was prebaked at 90 ° C for 60 seconds. A cured film having a film thickness of 1.2 μm was obtained.
Then, using a exposure apparatus (manufactured by TOPCON, TME150RTO), the coating film was exposed to an exposure amount of 40 mJ/cm ² via a photomask having a line and gap pattern of 10 μm (exposure by ultraviolet light of an ultrahigh pressure mercury lamp).
After the exposure, an aqueous solution of potassium hydroxide having a concentration of 0.05% by mass was used as a developing solution, and development was carried out at 25 ° C for 60 seconds.
The developed coated film after development was post-baked at 230 ° C for 30 + 180 minutes (total 210 minutes) to obtain a substrate Pg.

<pattern shape evaluation (defect, straightness, line cone angle)>
A line and gap pattern formed on the substrate Pg was observed by a scanning electron microscope S-9220 (manufactured by Hitachi, Ltd.), and any of the examples 1 to 3 and the comparative examples 1 to 5 was able to form a line and gap pattern, and it was confirmed. Each of the photosensitive compositions has a negative photosensitive composition which is sensitive to an exposure amount at an exposure amount of 40 mJ/cm ² or less.
Then, the pattern peeling defect, the linear straightness (mask faith), and the line taper angle were evaluated in more detail.
The pattern peeling defect was evaluated based on the observation results of 10 lines based on the following criteria.
○: No pattern peeling.
△: Among the 10 pieces, the number of the lines of peeling was observed to be one or two.
×: Among the 10 roots, the number of the lines of peeling was observed to be 3 to 10.
The straightness is evaluated based on the following criteria.
○: A straight pattern is formed.
×: Defects such as deformation, flaws, and lack of edges were observed.

The line taper angle is a cross section in the width direction of the line portion 10 of the cured product pattern of the photosensitive composition, and the angle θ formed by the side surface of the substrate 90a and the line portion 10 is measured as shown in Fig. 1 . Furthermore, in the case of the trapezoidal shape as shown in FIG. 1, θ exceeds 0 degrees and is less than 90 degrees, which is called a forward cone. Further, in the case of the inverted trapezoidal shape as shown in FIG. 2, θ exceeds 90 degrees and is less than 180 degrees, which is called an inverted cone. Regarding the line taper angle (pattern cross-sectional shape), evaluation was performed based on the following criteria.
◎: The measurement angle θ is 70 degrees or more and 85 degrees or less. ○: The measurement angle θ is 86 degrees or more and 90 degrees or less. Δ: The measurement angle θ is 91 degrees or more and 100 degrees or less ×: The measurement angle is 100 degrees or more. In FIGS. 1 and 2, the surface where the substrate 90a is in contact with the line portion 10 of the cured composition cured pattern is used as a reference surface, and the angle formed by the parallel line of the reference surface and the line side surface is expressed as θ. θ is the same.

<Line taper angle θ required for liquid crystal display panel>
Here, the line taper angle θ is supplemented. As the line taper angle θ, in order to ensure the faithfulness to the mask pattern, it is desirable to be 90 degrees. However, when a black matrix using a photosensitive composition is incorporated into an image display panel, liquid crystal and black matrix may be disposed in contact with each other.
In the liquid crystal system, the molecular alignment is controlled by a voltage, and in an optical system including a polarizing plate, display of characters, images, and the like is performed by changing the light transmittance drastically. When the liquid crystal and the black matrix are placed in contact with each other, the boundary of the pattern of the black matrix is affected by the boundary step, and the liquid crystal alignment behavior is different from the pattern flat portion (corresponding to the above-mentioned line portion or gap portion). As an optical phenomenon, even if the light transmittance of the flat portion of the pattern is 0%, light is transmitted through the boundary portion of the pattern, and is observed as light leakage or light leakage at the boundary portion of the pattern, and is used as an image display panel and an image display device. Not suitable.
This glazing phenomenon is remarkable when the line taper angle θ of the black matrix pattern exceeds 90 degrees, and is reduced when the line taper angle θ is 90 degrees or less. When the driving test is performed as the image display panel and the image display device, the line taper angle θ is 85 degrees or less, which is a suitable angle. In addition, if it is less than 70 degrees, the light transmission region is narrowed (in FIG. 1, the gap portion other than the line portion 10 is narrowed), and the amount of light is reduced. Therefore, it is not suitable as an image display panel and a video display device.
Therefore, as the liquid crystal display panel and the liquid crystal display device, the taper angle θ is preferably 90 degrees or less, and most preferably 70 degrees or more and 85 degrees or less.

[Table 2]
*1 120 ° C, 2 atmospheres, 36 hours after treatment
*2 120 ° C, 2 atmospheres, 1 hour after treatment

According to Tables 1 and 2, when an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and an opacifier (D) are contained, an oxime ester compound having a specific structure is used ( C1) As the photopolymerization initiator (C), the photosensitive compositions of Examples 1 to 3 containing the resin-coated carbon black (D1) as the light-shielding agent (D) can form a higher unit optical density (3.8). /μm) and a higher volume resistance value (1.0 × 10 ¹³ Ω · m or more, more preferably 1.0 × 10 ¹⁴ Ω · m or more), and have good adhesion to the substrate and a good pattern shape (defect, Patterned cured film with straightness, line taper angle θ).

On the other hand, in the case of using the photosensitive compositions of Comparative Examples 1 to 4 which do not contain the compound satisfying the oxime ester compound (C1), only the adhesion to the substrate, the volume resistivity, and the pattern shape (defects) can be formed. A cured film which is insufficient in any of straightness and taper angle θ).

1‧‧‧Image display panel

10‧‧‧Lighting layer

20a, 20b, 20c‧‧‧ colored layer

30‧‧‧Liquid layer

40‧‧‧ wiring

50a, 50b‧‧‧ polarizing layer

90a‧‧‧CF support substrate

90b‧‧‧TFT support substrate

100‧‧‧Color filters

Fig. 1 is a view schematically showing a cross-sectional shape in a pattern width direction of a cured film (black matrix) formed using a photosensitive composition having a cross-sectional shape of a forward taper.

2 is a view schematically showing a cross-sectional shape in the pattern width direction of a cured film (black matrix) formed using a photosensitive composition having a cross-sectional shape of an inverted cone.

Fig. 3 is a view schematically showing a cross section of a color filter formed using a photosensitive composition and an image display panel 1 formed using the color filter.

Claims (12)

A photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and an opacifier (D), and the photopolymerization initiator (C) Containing the oxime ester compound (C1) represented by the following formula (c1): [Chemical Formula 1] (In the formula (c1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, R ³ is a monovalent organic group, and R ⁴ is a monovalent organic group. R ⁵ and R ⁶ are each independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and m1, m2 and m3 are each 0 or 1), and the above oxime ester compound (C1) satisfies the following (1) to (3) at least one of the conditions: (1) R ¹ contains a group represented by -OR ⁷ , R ⁷ is a haloalkyl group (2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a halogen. The alkyl group (3) R ³ is a branched alkyl group which may have a substituent, and the above-mentioned sunscreen agent (D) contains a resin-coated carbon black (D1). The photosensitive composition of claim 1, wherein the oxime ester compound (C1) is a compound represented by the following formula (c1-III): [Chemical 2] (In the formula (c1-III), R ¹ , R ² , R ³ , R ⁴ , m1, m2 and m3 are the same as the above formula (c1)). The photosensitive composition of claim 1 or 2, wherein the photopolymerization initiator (C) further contains an aminoalkylphenone compound (C2). The photosensitive composition of claim 1 or 2, wherein the resin-coated carbon black (D1) contains an epoxy-coated carbon black (D1). The photosensitive composition of Claim 1 or 2, wherein the content of the photopolymerization initiator (C) is 1% by mass or more and 15% by mass or less based on the mass of the solid content component of the photosensitive composition. The photosensitive composition of Claim 1 or 2, wherein the content of the above-mentioned oxime ester compound (C1) is 30% by mass or more based on the mass of the photopolymerization initiator (C). A hardened material which is a cured product of the photosensitive composition of any one of claims 1 to 6. A color filter comprising a black matrix comprising a cured material as claimed in claim 7. An image display panel having a color filter as claimed in claim 8. An image display device comprising the image display panel of claim 9. A method of manufacturing a patterned cured film, comprising: Applying the photosensitive composition according to any one of claims 1 to 6 to form a coating film on the substrate, Positionally selectively exposing the coating film, and The exposed coated film was developed. The manufacturing method of claim 11, wherein the patterned hardened film is a black matrix.