JP2019120768A - Photosensitive composition, cured article, cured article formation method, color filter, and image display device - Google Patents

Abstract

To provide a photosensitive composition excellent in shading property and insulation property, and capable of forming a cured film with a desired cross section shape, a cure article of the photosensitive composition, a color filter having a black matrix consisting of the cured article, an image display panel having the color filter, an image display device having the image display panel, and a manufacturing method of a patterned cured film using the photosensitive composition.SOLUTION: In a photosensitive composition containing a shading agent, an oxime ester compound with a specific structure is used as a photoinitiator, and a resin coated carbon black is used as the shading agent.SELECTED DRAWING: None

Description

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

  In a panel for a display such as a liquid crystal display, a patterned light-shielding film such as a black matrix or a black column spacer is usually formed. Various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator, which are used to form a light-shielding film in such applications, have been proposed.

  For example, as a material for forming a black matrix, a negative photosensitive resin 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 Resin compositions have been proposed (see Patent Document 1).

JP, 2011-170075, A

By the way, in the panel for image display devices, the image quality is improved daily. For this reason, the black matrix is required to further improve the light shielding property from the viewpoint of improving the contrast and the like. For example, when forming a black matrix using a photosensitive resin composition as described in Patent Document 1, the black matrix formed by increasing the content of carbon black in the photosensitive resin composition The light shielding property can be improved.
However, when the content of carbon black in the photosensitive resin composition is increased, the insulation (resistance value) of the black matrix to be formed is lowered, or curing defects due to the decrease in sensitivity of the photosensitive resin composition are caused. As a result, it may be difficult to form a black matrix having a desired cross-sectional shape.

  The present invention has been made in view of the above problems, and has a photosensitive composition excellent in light shielding property and insulating property and capable of forming a cured film having a desired cross-sectional shape, and a cured product of the photosensitive composition. A color filter comprising a black matrix comprising the cured product, an image display panel comprising the color filter, an image display device comprising the image display panel, and a patterned cured film using the photosensitive composition described above The purpose is to provide a manufacturing method.

  As a result of intensive studies, the present inventors have used an oxime ester compound having a specific structure as a photopolymerization initiator in a photosensitive composition containing a light shielding agent, and using resin-coated carbon black as a light shielding agent. The present invention has been found out that the above problems can be solved.

（式（ｃ１）中、Ｒ^１は、１価の有機基であり、Ｒ^２は、置換基を有してもよい炭化水素基、又は置換基を有してもよいヘテロシクリル基であり、Ｒ^３は、１価の有機基であり、Ｒ^４は、１価の有機基であり、Ｒ^５、及びＲ^６はそれぞれ独立に、置換基を有してもよいベンゼン環、又は置換基を有してもよいナフタレン環であり、ｍ１、ｍ２、及びｍ３はそれぞれ０又は１である。）
で表されるオキシムエステル化合物（Ｃ１）を含み、
オキシムエステル化合物（Ｃ１）が、下記（１）〜（３）：
（１）Ｒ^１が−ＯＲ^７で表される基を含み、Ｒ^７がハロゲノアルキル基である
（２）ｍ２が１であり、Ｒ^４が−ＯＲ^７で表される基を含み、Ｒ^７がハロゲノアルキル基である
（３）Ｒ^３が置換基を有してもよい分岐鎖状アルキル基である
の少なくとも１つの条件を満たし、
遮光剤（Ｄ）が、樹脂被覆カーボンブラック（Ｄ１）を含む、感光性組成物である。 A first aspect of the present invention is a photosensitive composition comprising an alkali soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D),
The photopolymerization initiator (C) has the following formula (c1):

(In formula (c1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent, or a heterocyclyl group which may have a substituent, R ³ is a monovalent organic group, R ⁴ is a monovalent organic group, and R ⁵ and R ⁶ each independently have a benzene ring which may have a substituent, or a substituent Naphthalene ring, and m1, m2 and m3 are each 0 or 1)
Containing an oxime ester compound (C1) represented by
The oxime ester compound (C1) comprises the following (1) to (3):
(1) R ¹ includes a group represented by —OR ⁷ , R ⁷ is a halogenoalkyl group (2) m 2 is 1 and R ⁴ includes a group represented by —OR ⁷ , R ⁷ At least one of the following conditions: is a halogenoalkyl group (3) R ³ is a branched alkyl group which may have a substituent, and
It is a photosensitive composition in which the light shielding agent (D) contains a resin-coated carbon black (D1).

  A second aspect of the present invention is a cured product of the photosensitive composition according to the first aspect.

  A third aspect of the present invention is a color filter provided with a black matrix comprising a cured product of the photosensitive composition according to the second aspect.

  A fourth aspect of the present invention is an image display panel comprising the color filter according to the third aspect.

  A fifth aspect of the present invention is an image display device comprising the image display panel according to the fourth aspect.

According to a sixth aspect of the present invention, there is provided a method of applying a photosensitive composition according to the first aspect onto a substrate to form a coating film.
Position-selective exposure of the coating film,
Developing the exposed coating film,
A method of producing a patterned cured film comprising:

  According to the present invention, the photosensitive composition having excellent light shielding properties and insulating properties and capable of forming a cured film having a desired cross-sectional shape, a cured product of the photosensitive composition, and a black matrix composed of the cured product A color filter, an image display panel provided with the color filter, an image display device provided with the image display panel, and a method for producing a patterned cured film using the photosensitive composition described above can be provided.

It is a figure which shows typically the cross-sectional shape of the pattern width direction of the cured film (black matrix) formed using the photosensitive composition provided with the cross-sectional shape of a normal taper. It is a figure which shows typically the cross-sectional shape of the pattern width direction of the cured film (black matrix) formed using the photosensitive composition provided with cross-sectional shape of reverse taper. It is a figure which shows typically the cross section of the color filter formed using the photosensitive composition, and the image display panel 1 formed using the said color filter.

«Photosensitive composition»
The photosensitive composition contains an alkali soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D). A photoinitiator (C) contains the oxime ester compound (C1) of the specific structure mentioned later. The light shielding agent (D) contains a resin-coated carbon black (D1). The photosensitive composition may also contain components such as an additive (E) and an organic solvent (S), if necessary.

The thickness of the cured film formed using the photosensitive composition is not particularly limited. The thickness of the cured film is preferably 0.2 μm or more, more preferably 0.3 μm to 5 μm, still more preferably 0.4 μm to 3 μm, and particularly preferably 0.5 μm to 2 μm.
Hereinafter, an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D) which are essential components contained in the photosensitive composition, and optional components, The manufacturing method of photosensitive composition hardened | cured material is demonstrated.

<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 conventionally contained in various photosensitive resin compositions.
Here, in the present specification, the alkali-soluble resin (A) refers to a resin provided with a functional group (for example, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) that causes alkali solubility in the molecule.

As resin suitable as alkali-soluble resin (A), resin (a-1) (Hereafter, it is described also as "cardo resin (a-1).") Which has a cardo structure is mentioned.
When using a resin (a-1) having a cardo structure as the alkali-soluble resin, it is easy to obtain a photosensitive composition having excellent resolution, and a photosensitive composition is used to form a cured film that does not easily flow excessively. Cheap. For this reason, it is easy to form a favorable cured film of cross-sectional shape.

[Resin having cardo structure (a-1)]
As resin (a-1) which has cardo frame | skeleton, it has cardo frame | skeleton in the structure, and resin which has predetermined alkali solubility can be used. 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. Note that the second annular structure and the third annular structure may have the same structure or different structures.
A representative example of the cardo skeleton is a skeleton in which two aromatic rings (eg, benzene rings) are bonded to the carbon atom at position 9 of the fluorene ring.

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

In formula (a-1), X ^a represents a group represented by the following formula (a-2). t1 represents an integer of 0 or more and 20 or less.

In the above formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group. ^{shown, R a3} each independently represent an alkylene group of straight or branched chain, t2 is 0 or 1, ^{W a} represents a group represented by the following formula (a3).

In the formula (a-2), as R ^a3 , an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 6 carbon atoms Particular preference is given to ethane-1,2-diyl, propane-1,2-diyl and propane-1,3-diyl.

Ring A in Formula (a-3) represents an aliphatic ring which may be fused with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle.
Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like.
Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring which may be fused to the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

The following groups are mentioned as a suitable example of a bivalent group denoted by a formula (a-3).

The divalent group X ^a in the formula (a-1) is a cardo by reacting a tetracarboxylic acid dianhydride giving the residue Z ^a with a diol compound represented by the following formula (a-2 a) It is introduced into the resin (a-1).

In Formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and t2 are as described for Formula (a-2). The ring A in the formula (a-2a) is as described for the formula (a-3).

The diol compound represented by formula (a-2a) can be produced, for example, by the following method.
First, after substituting a hydrogen atom in a phenolic hydroxyl group possessed by a diol compound represented by the following formula (a-2b), as necessary, into a group represented by -Ra ³ -OH according to a conventional method, It glycidylizes using epichlorohydrin etc. and obtains the epoxy compound represented by a following formula (a-2c).
Subsequently, the diol compound represented by Formula (a-2a) is obtained by making the epoxy compound represented by Formula (a-2c) react with acrylic acid or methacrylic acid.
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 Formula (a-2b) and Formula (a-2c) is as described for Formula (a-3).
In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to said method.

The following diol compounds are mentioned as a suitable example of a diol compound denoted by a formula (a-2b).

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 the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Phthalic anhydride, glutaric anhydride and the like can be mentioned.

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

（式（ａ−４）中、Ｒ^ａ４、Ｒ^ａ５、及びＲ^ａ６は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｔ３は、０以上１２以下の整数を示す。）

(In 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 to 10 carbon atoms, and a fluorine atom , And t3 represents an integer of 0 or more and 12 or less.)

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

As R ^a4 in the formula (a-4), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferably each independently from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. R ^a4 in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
A plurality of R ^a4 in the formula (a-4) is preferably the same group because preparation of high purity tetracarboxylic acid dianhydride is easy.

T3 in Formula (a-4) represents an integer of 0 or more and 12 or less. By setting the value of t3 to 12 or less, purification of tetracarboxylic acid dianhydride can be facilitated.
The upper limit of t3 is preferably 5 and more preferably 3 from the viewpoint of easy purification of tetracarboxylic dianhydride.
From the viewpoint of chemical stability of tetracarboxylic dianhydride, the lower limit of t3 is preferably 1, and more preferably 2.
T3 in Formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms which can be selected as R ^a5 and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ^a4 .
^{Each of} R ^a5 and R ^a6 is a hydrogen atom, or having 1 to 10 carbon atoms (preferably 1 to 6 and more preferably 1 to 5), from the viewpoint of easy purification of tetracarboxylic acid dianhydride. More preferably, it is an alkyl group of 1 or more and 4 or less, particularly preferably 1 or more and 3 or less), and a hydrogen atom or a methyl group is particularly preferable.

  As the tetracarboxylic acid dianhydride represented by the formula (a-4), for example, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ′ ′-norbornane-5,5 ′ ′ 6,6 ′ ′-tetracarboxylic acid dianhydride (also known as “norbornane-2-spiro-2′-cyclopentanone-5′-spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 ′ ′) -Tetracarboxylic acid dianhydride "), methyl norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-(methyl norbornane) -5,5 '', 6,6 ''-tetra Carboxylic acid dianhydride, norbornane-2-spiro-α-cyclohexanone-α′-spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride (also known as “norbornane- 2-spiro-2'-shik Hexanone-6'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid dianhydride "), methyl norbornane-2-spiro-α-cyclohexanone-α'-spiro- 2 ′ ′-(methyl norbornane) -5,5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopropanone-α′-spiro-2 ′ ′-norbornane -5,5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclobutanone-α′-spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 '' -Tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2 ''-norbornane-5,5 ', 6,6'-tetracarboxylic acid dianhydride Object, norbornane -2- Pyro-α-cyclooctanone-α′-spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclononanone-α ′ -Spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclodecanone-α′-spiro-2 ′ ′-norbornane-5 , 5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cycloundecanone-α′-spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 '' -Tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2 ''-norbornane-5,5 ', 6,6'-tetracarboxylic acid dianhydride , Norbornane-2-spiro -Α-Cyclotridecanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclotetradecanone- α′-spiro-2 ′ ′-norbornane-5,5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α′-spiro-2 ′ '-Norborane-5,5' ', 6,6' '-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'-spiro-2' '-norbornane-5 , 5 ′ ′, 6,6 ′ ′-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α′-spiro-2 ′ ′-norbornane-5,5 ′ ′ 6, 6 ''-tetracarboxylic acid dianhydride Etc. The.

  The weight average molecular weight of the cardo resin (a-1) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, and still more preferably 2000 or more and 10000 or less. By setting it as said range, sufficient heat resistance and mechanical strength can be obtained about a cured film, obtaining favorable developability.

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

(Phenols)
As phenols used when producing novolak resin (a-2), for example, phenol; cresols such as o-cresol, m-cresol, p-cresol, etc .; 2,3-xylenol, 2,4-xylenol Xylenols such as 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethyl phenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; 2 Alkylphenols such as isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol, and 3,4 5-trimethyl-f Trialkylphenols such as phenol; resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and polyphenols such as phlorogricinol; alkylresorcinol, alkyl catechols, alkyl polyphenols such as alkyl hydroquinone (any alkyl A group is also 1 or more and 4 or less carbon atoms.); Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various properties such as heat resistance of the black matrix formed using the photosensitive composition can be adjusted by adjusting the mixing ratio of the two.
Although the compounding ratio of m-cresol and p-cresol is not particularly limited, the molar ratio of m-cresol / p-cresol is preferably 3/7 to 8/2. By using m-cresol and p-cresol in such a ratio, it is easy to obtain a photosensitive composition capable of forming a black matrix excellent in heat resistance.

In addition, novolak resins produced by using m-cresol in combination with 2,3,5-trimethylphenol are also preferable. In the case of using such novolak resin, it is particularly easy to obtain a photosensitive composition capable of forming a black matrix which is less likely to flow excessively by heating at post-baking.
Although the compounding ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, it is preferably 70/30 or more and 95/5 or less in terms of a molar ratio of m-cresol / 2,3,5-trimethylphenol.

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

(Acid catalyst)
As an acid catalyst used when producing the novolak resin (a-2), for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and And organic acids such as para-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular weight)
The polystyrene equivalent weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the novolak resin (a-2) is the resistance to flow by heating of the black matrix formed using the photosensitive composition. From the viewpoint, the lower limit is preferably 2000, more preferably 5000, particularly preferably 10000, still more preferably 15000, most preferably 20000, the upper limit is preferably 50000, more preferably 45000, still more preferably 40000, most preferably 35000 preferable.

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

[Modified epoxy resin (a-3)]
As the alkali-soluble resin (A), higher flow resistance at the time of baking is realized, and an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (from the viewpoint of easily imparting high water resistance to the cured film) The polybasic acid anhydride (a-3c) adduct (a-3) of the reaction product with a-3b) may be included. Such an adduct is also referred to as "modified epoxy resin (a-3)".
In the specification and claims of the present application, a compound which falls under the above definition and which does not fall under the resin (a-1) having the cardo structure described above is a modified epoxy resin (a-3) And).

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

<Epoxy Compound (a-3a)>
The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and it may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound having no aromatic group. Well, aromatic epoxy compounds having an aromatic group are preferred.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a bifunctional or higher polyfunctional epoxy compound, and is preferably a polyfunctional epoxy compound.

  Specific examples of the epoxy compound (a-3a) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, and biphenyl epoxy resin Functional epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene diamine, tetraglycidyl bisaminomethyl cyclohexane and the like Glycidyl amine type epoxy resin; Heterocyclic epoxy resin such as triglycidyl isocyanurate; Phloroglycinol triglycidyl ether, trihydroxy bif Nyltriglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2) , 3-Epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4] -(2,3-Epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] trifunctional epoxy resin such as propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetra Such as glycidyl ether and tetraglycidoxybiphenyl Functional epoxy resins.

Moreover, as an epoxy compound (a-3a), the epoxy compound which has a biphenyl skeleton is preferable.
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 capable of forming a cured film excellent in balance between sensitivity and developability and excellent in adhesion to a substrate.

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

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

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

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

When R ^a7 is a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0-5, preferably 0 or 1.
Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro Groups are mentioned.

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

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

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

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

(Unsaturated group-containing carboxylic acid (a-3b))
In preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) are reacted.
As unsaturated group containing carboxylic acid (a-3b), the monocarboxylic acid which contains reactive unsaturated double bonds, such as an acryl group and a methacryl group, in a molecule | numerator is preferable. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, cinnamic acid and the like. The unsaturated group-containing carboxylic acids (a-3b) may be used alone or in combination of two or more.

  The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferable reaction method, for example, an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b), a tertiary amine such as triethylamine or benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, Using tetraethyl ammonium chloride, quaternary ammonium salt such as benzyl triethyl ammonium chloride, pyridine, or triphenyl phosphine as a catalyst, the reaction is carried out in an organic solvent at a reaction temperature of 50 ° C. to 150 ° C. for several hours to several tens of hours Be

The ratio of the amount of the two used in the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) is the epoxy equivalent of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid ( As a ratio with the carboxylic acid equivalent of a-3 b), normally 1: 0.5 to 1: 2 are preferable, 1: 0.8 to 1: 1.25 are more preferable, 1: 0.9 to 1: 1. .1 is particularly preferred.
When the ratio of the used amount of the epoxy compound (a-3a) to the used amount of the unsaturated group-containing carboxylic acid (a-3b) is 1: 0.5 to 1: 2 in the above equivalent ratio, the crosslinking efficiency is Tend to improve, which is preferable.

(Polybasic acid anhydride (a-3c))
The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups.
Examples of the polybasic acid anhydride (a-3c) include, but are not limited to, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydroanhydride, etc. Phthalic acid, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexa Hydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride And the following formula (a-3c-1) Compounds, and represented by may be a compound with the following formula (a-3c-2). Moreover, you may use polybasic acid anhydride (a-3c) individually or in combination of 2 or more types.

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

(In formula (a-3c-2), R ^a8 represents an alkylene group which may have a substituent of 1 to 10 carbon atoms.)

  The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings, because it is easy to obtain a photosensitive composition excellent in the balance between sensitivity and developability. In addition, the polybasic acid anhydride (a-3c) includes at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2) Is more preferred.

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

  The acid value of the modified epoxy resin (a-3) is preferably 10 mg KOH / g to 150 mg KOH / g, and more preferably 70 mg KOH / g to 110 mg KOH / g, in terms of resin solid content. When the acid value of the resin is 10 mg KOH / g or more, sufficient solubility in the developer can be obtained, and when the acid value is 150 mg KOH / g or less, sufficient curability can be obtained, and the surface properties are improved. It can be good.

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

[Acrylic resin (a-4)]
Acrylic resin (a-4) is also preferable as a component which comprises alkali-soluble resin (A).
As acrylic resin (a-4), resin containing the structural unit derived from (meth) acrylic acid and / or the structural unit derived from other monomers, such as (meth) acrylic acid ester, can be used. (Meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester 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.

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. The organic group may be linear, branched or cyclic.

The substituent other than the hydrocarbon group in the organic group of R ^a10 is not particularly limited as long as the effects of the present invention are not impaired, and a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxy imino group, alkyl imino group, alkyl ether group, alkyl thio ether group, aryl ether group, aryl thio ether group, amino group (-NH ₂ , -NHR, -NRR ': R and R ′ each independently represents a hydrocarbon group) and the like. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. The hydrocarbon group contained in the above-mentioned substituent may be linear, branched or cyclic.

The organic group as R ^a10 is acryloyloxy group, methacryloyloxy group, an epoxy group, may have a reactive functional group such as oxetanyl group.
An acyl group having an unsaturated double bond or the like, such as an acryloyloxy group or a methacryloyloxy group, is, for example, at least a part of an epoxy group in an acrylic resin (a-4) containing a structural unit having an epoxy group It can be produced by reacting an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

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

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

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

As a specific example of a compound represented by a formula (a-4-1) when a compound represented by a formula (a-4-1) has a chain-like group which has an epoxy group as ^Ra10 , (Meth) acrylic acid epoxy alkyl esters such as glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate .

  Moreover, an alicyclic epoxy group containing (meth) acrylic acid ester may be sufficient as the compound represented by Formula (a-4-1). The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. In addition, examples of the polycyclic alicyclic group include norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group and the like.

  As a specific example in the case where a compound represented by a formula (a-4-1) is an alicyclic epoxy group containing (meth) acrylic acid ester, for example, the following formulas (a-4-1a) to (a-4) And a compound represented by -1o). Among these, in order to bring developability into an appropriate range, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferable, and the following formula (a-4-1a) is preferable. The compounds represented by (a) to (a-4-1c) are more preferable.

In the above formulae, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents 1 to 10 carbon atoms. Is a hydrocarbon group having a valency of t, and t is an integer of 0 or more and 10 or less. As R ^a21 , a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group is preferable. The R ^a22, for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, a phenylene group, cyclohexylene _group, -CH 2 _-Ph-CH 2 - is (Ph Phenylene group is preferred).

  Moreover, the copolymer which further polymerized monomers other than (meth) acrylic acid ester may be sufficient as acrylic resin (a-4). Examples of monomers other than (meth) acrylic acid esters include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These monomers can be used alone or in combination of two or more.

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

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

  As allyl compounds, allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; etc. It can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butyl aminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

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

  As styrenes, styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy Alkylstyrenes such as methylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

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

When acrylic resin (a-4) has a structural unit which has unsaturated double bond, the quantity of the structural unit which has unsaturated double bond in acrylic resin (a-4) is 1 mass% or more 50 mass% or less is preferable, 1 mass% or more and 30 mass% or less are more preferable, and 1 mass% or more and 20 mass% or less are especially preferable.
When the acrylic resin (a-4) contains a structural unit having an unsaturated double bond in an amount within the above range, the acrylic resin can be incorporated into the crosslinking reaction in the resist film and made uniform, which is a cured film. Is effective in improving the heat resistance and mechanical properties of

  The weight average molecular weight of the acrylic resin (a-4) is preferably 2,000 or more and 50,000 or less, and more preferably 3,000 or more and 30,000 or less. By setting it in the above-mentioned range, the balance between the film forming ability of the photosensitive composition and the developability after exposure tends to be easily obtained.

  The content of the alkali-soluble resin (A) is preferably 10% by mass to 65% by mass, and more preferably 15% by mass to 50% by mass, with respect to the total mass of the photosensitive composition. More preferable. By setting it as said range, it is easy to obtain the photosensitive composition which is excellent in developability.

<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 monofunctional monomers and polyfunctional monomers.

  Examples of monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido- 2-Methylpropanesulfonic acid, tert-butyl acrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2 -Trifluoroethyl (meth) acrylate, 2,2,3,3- tetrafluoropropyl (meth) acrylate, the half (meth) acrylate of a phthalic acid derivative, etc. are mentioned. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as polyfunctional monomers, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate , 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate ) Acrile Tripropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene-propylene) glycol di (meth) acrylate, polytetramethylene glycol di (meth) ) Acrylate, Ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butyrene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxypheny B) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate , Diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate, trimethylhexa) Methylene diisocyanate or a reaction product of hexamethylene diisocyanate etc. with 2-hydroxyethyl (meth) acrylate), methylene bis (meth) acrylamide, (meth Acrylamide methylene ether, condensation product of polyhydric alcohol and N-methylol (meth) acrylamide, triacrylic formal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-tris Ethanol triacrylate and 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate etc. are mentioned. These polyfunctional monomers can be used alone or in combination of two or more.

Among these compounds having an ethylenically unsaturated double bond, a polyfunctional monomer having two or more functions is preferable from the viewpoint that a photosensitive composition giving a cured product excellent in strength and adhesion to a substrate can be obtained. Among these, trifunctional or higher polyfunctional monomers are particularly preferable. For example, pentaerythritol tetra (meth) acrylate (tetrafunctional monomer), dipentaerythritol penta (meth) acrylate (pentafunctional monomer), and dipentaerythritol hexa (meth) acrylate (hexafunctional monomer) are suitably used.
From the viewpoint of control of the glass transition point (Tg), monofunctional monomers or bifunctional monomers may be used in combination with a trifunctional or higher polyfunctional monomer, and among these, 1,6-hexanediol di (meth) Acrylate is preferred.

  The content of the photopolymerizable monomer (B) in the photosensitive composition is preferably from 1% by mass to 50% by mass, and more preferably from 5% by mass to 40% by mass, based on the mass of the entire solid content of the photosensitive composition. Is more preferred. By setting the above range, balance between sensitivity, developability and resolution tends to be easily obtained.

<Photoinitiator (C)>
A photosensitive composition contains the oxime ester compound (C1) represented by Formula (c1) mentioned later as a photoinitiator (C). Hereinafter, the oxime ester compound (C1) will be described.

（式（ｃ１）中、Ｒ^１は、１価の有機基であり、Ｒ^２は、置換基を有してもよい炭化水素基、又は置換基を有してもよいヘテロシクリル基であり、Ｒ^３は、１価の有機基であり、Ｒ^４は、１価の有機基であり、Ｒ^５、及びＲ^６はそれぞれ独立に、置換基を有してもよいベンゼン環、又は置換基を有してもよいナフタレン環であり、ｍ１、ｍ２、及びｍ３はそれぞれ０又は１である。）
で表され、下記（１）〜（３）：
（１）Ｒ^１が−ＯＲ^７で表される基を含み、Ｒ^７がハロゲノアルキル基である。
（２）ｍ２が１であり、Ｒ^４が−ＯＲ^７で表される基を含み、Ｒ^７がハロゲノアルキル基である。
（３）Ｒ^３が置換基を有してもよい分岐鎖状アルキル基である。
のうちの少なくとも１つの条件を満たす化合物である。 [Oxime ester compound (C1)]
The oxime ester compound (C1) has the following formula (c1):

(In formula (c1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent, or a heterocyclyl group which may have a substituent, R ³ is a monovalent organic group, R ⁴ is a monovalent organic group, and R ⁵ and R ⁶ each independently have a benzene ring which may have a substituent, or a substituent Naphthalene ring, and m1, m2 and m3 are each 0 or 1)
Is represented by the following (1) to (3):
(1) R ¹ includes a group represented by —OR ⁷ and R ⁷ is a halogenoalkyl group.
(2) m2 is 1, R ⁴ includes a group represented by —OR ⁷ , and R ⁷ is a halogenoalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
A compound that satisfies at least one of

In formula (c1), R ⁵ and R ⁶ each represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
The ring containing a nitrogen atom bonded to R ³ shown in the formula (c1) and a benzene ring or a naphthalene ring are fused by sharing any carbon-carbon bond in the benzene ring or the naphthalene ring .
For this reason, the ring containing a nitrogen atom bonded to R ³ in the formula (c1) has a ring structure comprising a nitrogen atom, two carbon atoms derived from R ⁵ , and two carbon atoms derived from R ⁶ It is a 5-membered ring that is an atom.
That is, the compound represented by the formula (c1) has a tricyclic to pentacyclic fused ring composed of R ⁵ and R ⁶ and the above-mentioned 5-membered ring as a central skeleton.

When R ⁵ and / or R ⁶ is a naphthalene ring, the form of condensation of the above-mentioned 5-membered ring containing a nitrogen atom bonded to R ³ with the naphthalene ring is not particularly limited.
When at least one of R ⁵ and R ⁶ is a naphthalene ring, a fused ring consisting of R ⁵ and R ⁶ and the above 5-membered ring containing a nitrogen atom bonded to R ³ is any of the following: May be

When the benzene ring as R ⁵ and R ⁶ or the naphthalene ring has a substituent, the type and number of the substituents are not particularly limited as long as the object of the present invention is not impaired.
Preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, and 2 or more carbon atoms. A monoalkylamino group having an alkoxycarbonyl group having 7 or less carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms A dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, a halogen atom, a cyano group, etc. are mentioned.
When the benzene ring as R ⁵ and R ⁶ or the naphthalene ring has a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, and is preferably 1 or more and 4 or less. When there are a plurality of substituents, the plurality of substituents may be the same or different.

When R ⁵ has a substituent, the substituent that R ⁵ has may be combined with R ¹ or R ³ to form a ring.
Also, if R ⁶ has a substituent, the substituents R ⁶ has, or may be R ³ are bonded to form a ring.

The ring formed by combining the substituent that R ⁵ has with R ¹ may be a hydrocarbon ring or a heterocycle. The hetero atom contained in the said heterocyclic ring is not specifically limited. Preferred hetero atoms include N, O, S and the like.
The ring formed by bonding the substituent that R ⁵ and / or R ⁶ has to R ³ may contain another hetero atom in addition to the nitrogen atom that bonds to R ³ . The hetero atom contained in the said heterocyclic ring is not specifically limited. Preferred hetero atoms include N, O, S and the like.

（式（ｃ１−１−ａ）〜（ｃ１−１−ｈ）において、Ｒ^１、Ｒ^２、Ｒ^４、ｍ１、ｍ２、及びｍ３は式（ｃ１）と同様であり、Ｒ^８は、アルキル基である。）
で表される化合物が好ましい。 Substituents R ⁵ has, or the ^{substituents R 6} have, ^{if R 3} and are combined to form a ring, examples of the compound represented by formula (c1), the following formula (c1-1-a) ~ (C1-1-h):

(In the formulas (c1-1-a) to (c1-1-h), R ¹ , R ² , R ⁴ , m 1, m ² and m 3 are the same as in the formula (c 1), and R ⁸ is an alkyl group Is)
The compound represented by is preferable.

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

（式（ｃ１−１−ｉ）〜（ｃ１−１−ｌ）において、Ｒ^２、Ｒ^３、Ｒ^４、ｍ２、及びｍ３は式（ｃ１）と同様であり、Ｒ^８は、炭素原子数１以上２０以下のアルキル基である。）
で表される化合物が好ましい。Ｒ^８としてのアルキル基は、直鎖状であっても、分岐鎖状であってもよい。 When the substituent which R ⁵ has and R ¹ combine to form a ring, m 1 is preferably 0 in the formula (c 1). In this case, the compound represented by the formula (c1) has the following formulas (c1-1-i) to (c1-1-1):

(In the formulas (c1-1-i) to (c1-1-1), R ² , R ³ , R ⁴ , m ² and m 3 are the same as in the formula (c 1), and R ⁸ has 1 carbon atom More than 20 or less alkyl groups.)
The compound represented by is preferable. The alkyl group as R ⁸ may be linear or branched.

（式（ｃ１−Ｉ）〜（ｃ１−ＩＶ）において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｍ１、ｍ２、及びｍ３は式（ｃ１）と同様である。）
で表される化合物が好ましく、式（ｃ１−ＩＩ）、又は式（ｃ１−ＩＩＩ）で表される化合物がより好ましく、式（ｃ１−ＩＩＩ）で表される化合物が特に好ましい。 As the compound represented by the formula (c1) in consideration of the preferable combination of R ⁵ and R ⁶ described above, the compounds represented by the following formulas (c1-I) to (c1-IV):

(In the formulas (c1-I) to (c1-IV), R ¹ , R ² , R ³ , R ⁴ , m 1, m 2 and m 3 are the same as the formula (c 1).)
The compound represented by these is preferable, the compound represented by Formula (c1-II) or Formula (c1-III) is more preferable, and the compound represented by Formula (c1-III) is especially preferable.

As the compounds represented by the above formulas (c1-I) to (c1-IV), compounds represented by the following formulas (c1-I-a) to (c1-IV-a) are preferable, and The compound represented by II-a) or Formula (c1-III-a) is more preferable, and the compound represented by Formula (c1-III-a) is especially preferable.

As compounds represented by the above formulas (c1-I-a) to (c1-IV-a), compounds represented by the following formulas (c1-I-b) to (c1-IV-b) are preferable, The compound represented by Formula (c1-II-b) or Formula (c1-III-b) is more preferable, and the compound represented by Formula (c1-III-b) is especially preferable.

Examples of the monovalent organic group suitable as R ¹ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. A phenyl group which may be substituted, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy which may have a substituent Group, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, substituent A naphthoxycarbonyl group which may have, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a substituent A heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group and the like can be mentioned.

When R ¹ is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ¹ is an alkyl group, it may be linear or branched. When R ¹ is an alkyl group, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group etc. are mentioned. When R ¹ is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

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, and more preferably 1 or more and 6 or less. When R ¹ is an alkoxy group, it may be linear or branched. When R ¹ is an alkoxy group, specific examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, n Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ¹ is an alkoxy group, the alkoxy group may contain 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, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

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, and more preferably 3 or more and 6 or less. When R ¹ is a cycloalkyl group, specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of R ¹ being a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. When R ¹ is a saturated aliphatic acyl group, specific examples thereof include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Noyl group, and n-hexadecanoyl group etc. are mentioned. As specific examples in the case where R ¹ is a saturated aliphatic acyloxy group, acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

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, and more preferably 2 or more and 7 or less. Specific examples of R ¹ being an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples thereof include a sononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

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

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered single ring containing one or more of N, S and O, or such single rings or such single ring and benzene ring are condensed Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be either an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as the case where R ¹ is a heterocyclyl group.

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

When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ¹ further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms And a monoalkylamino group having the formula, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ¹ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, and is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group and the heterocyclyl 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 substituent which the phenylthioalkyl group may have are the same as the substituents which the phenyl group contained in R ¹ may have.

Among monovalent organic groups, R ¹ may be an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, even if it has a substituent on an aromatic ring Good phenylthioalkyl groups are preferred. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. preferable. Among the phenyl group which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. 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 particularly preferably 5 or 6. 1 or more and 8 or less are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkyl alkyl group, 1 or more and 4 or less are more preferable, and 2 is especially preferable. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1 or more and 8 or less are preferable, as for the carbon atom number of the alkylene group contained in the phenylthio alkyl group which may have a substituent on an aromatic ring, 1 or more and 4 or less are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

As described above, the compound represented by the formula (c1) is a compound represented by the following (1) to (3):
(1) R ¹ includes a group represented by —OR ⁷ and R ⁷ is a halogenoalkyl group.
(2) m2 is 1, R ⁴ includes a group represented by —OR ⁷ , and R ⁷ is a halogenoalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
It is necessary to meet at least one of
Therefore, R ¹ is preferably substituted by a substituent represented by —OR ⁷ . R ⁷ is a halogenoalkyl group. R ¹ is, when substituted with a group represented by -OR ^7, contained in R1, the number of the group represented by -OR ⁷ is not particularly limited. R ¹ is, when substituted with a group represented by -OR ^7, contained in ^{R 1,} the number of the group represented by -OR ⁷ is preferably 1 or 2, and more preferably 1.
In addition, the number of groups represented by -OR ⁷ in the compound represented by the formula (c1) is also preferably 1 or 2, and more preferably 1.

As a halogen atom contained in a halogeno alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. The halogenoalkyl group may contain one type of halogen atom, or may contain two or more types of halogen atoms in combination.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of halogen atoms contained in the halogenoalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the number of halogen atoms possessed by the halogenoalkyl group is preferably 7 or less, in that the compound represented by the formula (c1) has good compatibility with other components in the photosensitive composition, and 6 The following is more preferable, and 5 or less is particularly preferable.
In addition, the number of halogen atoms contained in the compound represented by the formula (c1) is also preferably 1 or more, more preferably 2 or more, particularly preferably 3 or more, preferably 7 or less, more preferably 6 or less, 5 or less Is particularly preferred.

The number of carbon atoms of the halogenoalkyl group is not particularly limited as long as the object of the present invention is not impaired. The carbon atom number of the halogenoalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the carbon atom number of the halogenoalkyl group is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.
As the halogenoalkyl group, a fluorinated alkyl group is particularly preferred. Preferred specific examples of the halogenoalkyl group include: 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3 And 3,3,3-pentafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl and the like. Among these, a 2,2,3,3-tetrafluoropropyl group is preferable because the production of the compound represented by the formula (c1) is easy.

（式（ｃ１−０１）中、Ｒ^７は前述の通りであり、Ｒ^９は、Ｒ^１としてのフェニル基が有してもよい置換基であり、ｍ４は１又は２であり、ｍ４＋ｍ５は１以上５以下の整数である。）
で表される基が好ましい。
Ｒ^９としては、炭素原子数１以上６以下のアルキル基、及び炭素原子数１以上６以下のアルコキシ基が好ましく、炭素原子数１以上６以下のアルキル基がより好ましく、メチル基、及びエチル基がさらに好ましく、メチル基が特に好ましい。
ｍ５は１であるのが好ましい。 As a group substituted by a halogenoalkyl group as R ¹ , a phenyl group substituted by one or two halogenoalkyl groups is preferable. Specifically, a group substituted with a halogenoalkyl group as R ¹ has the following formula (c1-01):

(In formula (c1-01), R ⁷ is as described above, R ⁹ is a substituent that may be possessed by a phenyl group as R ¹ , m 4 is 1 or 2, m 4 + m 5 is 1 It is an integer of 5 or less.)
The group represented by is preferable.
As R ⁹ , an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms are preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group and an ethyl group are more preferable. Is more preferred, and methyl is particularly preferred.
m5 is preferably 1.

（式（ｃ１−０２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、ｍ１、ｍ２、及びｍ３は式（ｃ１）と同様であり、Ｒ^１０は、２価の有機基である。）
で表される基であってもよい。 Moreover, R ¹ is a compound represented by the following formula (c1-02):

(In the formula (c1-02), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m 1, m 2 and m 3 are the same as in the formula (c 1), and R ¹⁰ is divalent) It is an organic group.)
It may be a group represented by

The divalent organic group as R ¹⁰ is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the divalent organic group as R ¹⁰ include alkanediyl groups having 1 to 10 carbon atoms (eg, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group) Butane-1,4-diyl group etc., and arylene groups (p-phenylene group, m-phenylene group, o-phenylene group, 1,1'-biphenyl-4,4 'diyl group etc.).

When R ¹ is a group represented by the above formula (c1-02), specific examples of the compound represented by the formula (c1) include compounds of the following formula.

Among R ¹ described above, a group represented by the following formula is preferable.

In formula (c1), R ² is a hydrocarbon group which may have a substituent or a heterocyclyl group which may have a substituent. The hydrocarbon group which may have a substituent is preferably an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As an aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is preferable. Preferred examples of the substituent which may be possessed when R ² is an alkyl group include a phenyl group and a naphthyl group. Further, as a substituent which may be possessed when R ² is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

When R ² is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ² is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered single ring containing one or more of N, S and O, or such single rings or such single ring and benzene ring are condensed Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. As the heterocyclic ring constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. Be
When R ² is a heterocyclyl group, examples of the substituent which the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group and the like.

As R ² , a methyl group, a phenyl group and a thienyl group are preferable, and a methyl group is more preferable.

In formula (c1), R ³ is a monovalent organic group. R ³ can be selected from various organic groups as long as the object of the present invention is not impaired. As preferable examples of R ³ , an alkyl group which may have a substituent having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, a carbon atom A saturated aliphatic acyl group which may have a substituent of 2 or more and 20 or less, an alkoxycarbonyl group which may have a substituent of 2 or more and 20 or less carbon atoms, and a phenyl group which may have a substituent A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a substituent A naphthyl group, a naphthoyl group which may have a substituent, a naphthoxy carbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a substituent Group which may have a group Ryl and heterocyclylcarbonyl which may have a substituent, etc. may be mentioned.

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

When R ³ has a substituent, preferable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. Group represented by the aliphatic acyl group, aliphatic acyloxy group having 2 to 20 carbon atoms, phenoxy group, benzoyl group, benzoyloxy group, -PO (OR) ₂ (R is 1 to 6 carbon atoms And the like), a halogen atom, a cyano group, a heterocyclyl group and the like. Preferred examples of the heterocyclyl group as a substituent are the same as the preferred examples of the heterocyclyl group as R ² .

As described above, the compound represented by the formula (c1) is a compound represented by the following (1) to (3):
(1) R ¹ includes a group represented by —OR ⁷ and R ⁷ is a halogenoalkyl group.
(2) m2 is 1, R ⁴ includes a group represented by —OR ⁷ , and R ⁷ is a halogenoalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
It is necessary to meet at least one of
Therefore, R ³ is preferably a branched alkyl group which may have a substituent.

（式（ｃ１−０３）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、ｍ１、ｍ２、及びｍ３は式（ｃ１）と同様であり、Ｒ^１１は２価の有機基である。） Moreover, as R ³ , the following formula (c1-03):

(In formula (c1-03), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , m 1, m 2 and m 3 are the same as in formula (c 1), and R ¹¹ is a divalent organic group .)

The divalent organic group as R ¹¹ is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the divalent organic group as R ¹¹ include alkanediyl groups having 1 to 10 carbon atoms (eg, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group) Butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc., arylene group p-phenylene group, m-phenylene group, o-phenylene group, 1,1'-biphenyl-4,4 'diyl group etc. are mentioned.

Also, the following group is also preferred as the divalent organic group as R ^11. In the following formulae, R ¹² is an alkylene group having 1 to 20 carbon atoms. Examples of the alkylene group as R ¹² include methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group are preferable.

When R ³ is a group represented by the above formula (c1-03), specific examples of the compound represented by the formula (c1) include compounds of the following formula.

Preferred specific examples of R ³ described above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, An isopentyl group, neopentyl group, pentan-3-yl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 2-ethylhexyl group can be mentioned.
As described above, since a branched alkyl group is preferable as R ³ , among the above alkyl groups, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, pentane-3 -Yl, sec-pentyl, tert-pentyl and 2-ethylhexyl are preferred.
Further, from the viewpoint of good solubility of the compound represented by formula (c1) in the photosensitive composition, n-octyl group and 2-ethylhexyl group are preferable, and 2-ethylhexyl group is more preferable.

R ⁴ in the formula (c1) is a monovalent organic group. Examples of the monovalent organic group as R ⁴ include the same groups as the monovalent organic group as R ¹ .

R ^{4 _{is, R 4 - (CO) m3}} - group represented by and bonded to the main skeleton of the compound represented by the formula (c1). R 4 _^- (CO) m3 ^- Specific preferable examples of the group represented by include groups represented by the following formula. In the following formula, m3 is 1 or 0 as in formula (c1).

The above ^R 4 - _{(CO) m3} - in the preferred examples of the group represented by the 1,3,5-trimethyl benzoyl group is particularly preferred.

As described above, the compound represented by the formula (c1) is a compound represented by the following (1) to (3):
(1) R ¹ includes a group represented by —OR ⁷ and R ⁷ is a halogenoalkyl group.
(2) m2 is 1, R ⁴ includes a group represented by —OR ⁷ , and R ⁷ is a halogenoalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
It is necessary to meet at least one of
For this reason, R ⁴ is preferably substituted by a substituent represented by —OR ⁷ . R ⁷ is a halogenoalkyl group. R ⁷ is as described above.

As a group substituted by a halogenoalkyl group as R ⁴ , a phenyl group substituted by one or two halogenoalkyl groups is preferable. Specifically, the group represented by the above-mentioned formula (c1-01) is preferable as in the case of the group substituted with a halogenoalkyl group as R ¹ .

（式（ｃ１−０４）中、Ｒ^１、Ｒ^３、Ｒ^５、Ｒ^６、ｍ１、ｍ２、及びｍ３は、式（ｃ１）と同一であり、Ｒ^１３は、２価の有機基である。）
で表される基も好ましい。 Moreover, as R ⁴ , the following formula (c1-04):

In formula (c1-04), R ¹ , R ³ , R ⁵ , R ⁶ , m 1, m 2 and m 3 are the same as in formula (c 1), and R ¹³ is a divalent organic group. )
Are also preferred.

The divalent organic group as R ¹³ is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the divalent organic group as R ¹³ include alkanediyl groups having 1 to 10 carbon atoms (eg, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group) Butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc., arylene group p-phenylene group, m-phenylene group, o-phenylene group, 1,1'-biphenyl-4,4 'diyl group etc. are mentioned.

Moreover, the following groups are also preferable as a divalent organic group as R ¹³ . In the following formulae, R ¹³ is an alkylene group having 1 to 20 carbon atoms which may be substituted by a halogen atom. As an alkylene group as R ¹⁴ , a methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group are preferable.
Further, a group in which all hydrogen atoms in these alkylene groups are substituted with a halogen atom, particularly a fluorine atom, is also preferable as R ¹⁴ .

  In formula (c1), m1, m2 and m3 are all 0 or 1. As m1, 0 is preferable. 1 is preferable as m2, and 1 is preferable as m3.

The following compounds are mentioned as a preferable specific example of a compound represented by Formula (c1) demonstrated above.

上述したように、式（ｃ１）で表される化合物は、下記（１）〜（３）：
（１）Ｒ^１が−ＯＲ^７で表される基を含み、Ｒ^７がハロゲノアルキル基である。
（２）ｍ２が１であり、Ｒ^４が−ＯＲ^７で表される基を含み、Ｒ^７がハロゲノアルキル基である。
（３）Ｒ^３が置換基を有してもよい分岐鎖状アルキル基である。
のうちの少なくとも１つの条件を満たす必要がある。この条件を満たせば２以上の異なる化合物を混合して光重合開始剤（Ｃ）として用いてもよい。

As described above, the compound represented by the formula (c1) has the following (1) to (3):
(1) R ¹ includes a group represented by —OR ⁷ and R ⁷ is a halogenoalkyl group.
(2) m2 is 1, R ⁴ includes a group represented by —OR ⁷ , and R ⁷ is a halogenoalkyl group.
(3) R ³ is a branched alkyl group which may have a substituent.
It is necessary to meet at least one of 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 the photopolymerization initiator (C). The oxime ester compound (C1) is excellent in the ability to absorb ultraviolet rays and generate radicals. For this reason, the oxime ester compound (C1) has high sensitivity, and even when it contains a high concentration of the light shielding agent (D), it is easy to sufficiently cure the photosensitive composition with a small exposure amount. In the case of a photosensitive composition containing a large amount of a light shielding agent (D), when the optical density of the film on which the photosensitive composition is formed is 3, the ultraviolet light exposure amount of the deep layer portion is 1/1000 of that of the surface layer portion (the outermost surface). When the optical density is 4, it is 1 / 10,000 of the surface layer (the outermost surface), but the oxime ester compound (C1) generates radicals even with such a relatively small amount of ultraviolet light exposure. , The photosensitive composition can be cured well.

Moreover, when the light shielding agent (D) mentioned later is mix | blended with a photosensitive composition in high concentration, the primary aggregate (aggregate) of a light shielding agent (D) is unavoidably unavoidable in the coating film which consists of a photosensitive composition. It occurs. However, in the case of using a photosensitive composition containing an oxime ester compound (C1) as the photopolymerization initiator (C), the photopolymerization initiator (C) is a radical upon irradiation with ultraviolet light even with a slight gap where the aggregates overlap intricately Generate
As a result, the cured product of the photosensitive composition is excellent not only in the adhesion to the substrate and in the electrical resistivity (insulation) under an environment of normal temperature and normal humidity and atmospheric pressure, but also the cured product has a high temperature, high humidity and high pressure environment. Adhesion to the substrate and the electrical resistivity (insulation) are less likely to decrease. The durability under a high temperature, high humidity, and high pressure environment can be confirmed by a so-called PCT test (pressure cooker test).
For this reason, in the image display panel using the black matrix which consists of hardened | cured material of the photosensitive composition containing an oxime ester compound (C1), the deterioration of performance does not produce it easily, even when the use environment is high temperature or humidity.

  A photoinitiator (C) may further contain photoinitiators other than oxime ester compound (C1) in the range which does not inhibit the objective of this invention. 20 mass% or more is preferable, as for the ratio of the mass of an oxime ester compound (C1) with respect to the mass of the whole photoinitiator (C), 30 mass% or more is more preferable, 35 mass% or more is still more preferable, 40 mass% The above is particularly preferable.

As a photoinitiator (C) other than an oxime ester compound (C1), an amino alkyl phenone type photoinitiator (C2) can be used suitably, for example.
As a preferable example of an amino alkyl phenone type photoinitiator (C2), the compound represented by a following formula (c2-1) is mentioned.

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

Preferred specific examples in the case where R ^c01 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n- A pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like can be mentioned. Among these, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group are preferable, Ethyl group is more preferred.

Preferred specific examples in the case where R ^c01 is a cycloalkyl group are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, And cyclododecyl groups.

Preferred specific examples where R ^c02 and R ^c03 are an alkyl group or a cycloalkyl group are the same as the preferred specific examples where R ^c01 is an alkyl group or a cycloalkyl group. As R ^c02 and R ^c03 , methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, An n-heptyl group and an n-octyl group are preferable, and a methyl group is more preferable.

When R ^c04 , R ^c05 , R ^c07 and R ^c08 are a halogen atom, specific examples include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like.
Preferred specific examples in the case where R ^c04 , R ^c05 , R ^c07 and R ^c08 are an alkyl group or a cycloalkyl group are the same as the preferred specific examples in the case where R ^c01 is an alkyl group or a cycloalkyl group .
When R ^c04 , R ^c05 , R ^c07 and R ^c08 are an alkoxy group, specific examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, sec -Butyloxy group and tert-butyloxy group can be mentioned.
As R ^c04 , R ^c05 , R ^c07 , and R ^c08 , ^hydrogen is ^{preferred because} it has good sensitivity and depth of focus of the photosensitive composition and it is easy to form a cured film with good adhesion to the substrate. An atom, a methyl group and an ethyl group are preferred, and a hydrogen atom is more preferred.

When R ^c06 is a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group, specific examples thereof are: R ^c04 , R ^c05 , R ^c07 and R ^c08 are a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group It is the same as the specific example in the case of.
The alkyl group as R ^{c0 6,} or alkyl group as R ^c06, cycloalkyl group and alkoxy groups, is, when substituted with one or more substituents, a hydroxyl group as the substituent, and methoxy group are preferred.

Preferable specific examples of R ^c06 include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-Hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, hydroxymethyl group, 2-hydroxyethyl group, methoxymethyl group, 2-methoxyethyl group, methoxy group, ethoxy group , N-propyloxy group, isopropyloxy group, n-butyloxy group, hydroxymethoxy group, 2-hydroxyethoxy group, methoxymethoxy group, 2-methoxyethoxy group and the like are preferable, and a hydrogen atom, a methyl group and an ethyl group are preferable. More preferable.

R ^c01 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group or an n-hexyl group ^c02 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, Or n-octyl group, and R ^c03 is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n - hexyl group, an n- heptyl group, and n- octyl ^{group, R c04} is a hydrogen atom, a methyl group, or ethyl ^{group, R c05} is a hydrogen atom, methyl Or ethyl ^{group, R c07} is a hydrogen atom, a methyl group, or ethyl ^{group, R c08} is a hydrogen atom, a methyl group, or ethyl ^{group, R c06} is methyl group, or a hydrogen atom Preferably there.

Examples of the aminoalkylphenone compound represented by the formula (c2-1) include 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (e.g. IRGACURE 369 manufactured by Specialty Chemicals, 2- (4-Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (eg manufactured by Ciba Specialty Chemicals) IRGACURE 379), 2- (4-ethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-isopropylbenzyl) -2- (dimethylamino)- 1- (4-morpholinophenyl) butan-1-one, 2- (4-n-butylbenzyl) -2- (dimethylamino) 1- (4-morpholinophenyl) butan-1-one, 2- (4-isobutylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4 -N-dodecylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (3,4-dimethylbenzyl) -2- (dimethylamino) -1- ( 4-morpholinophenyl) butan-1-one, 2- (4-methoxybenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-ethoxybenzyl) ) -2- (Dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-hydroxymethylbenzyl) -2- (dimethylamino) -1- (4-morpholino) 2- (4- (2-hydroxyethoxy) benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- [4- (phenyl) butan-1-one 2-Methoxyethoxy) benzyl] -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-isopropylbenzyl) -2-[(n-butyl) (methyl)] Amino] -1- (4-morpholinophenyl) butan-1-one, 2- (4-n-butylbenzyl) -2-[(n-butyl) (methyl) amino] -1- (4-morpholino Phenyl) butan-1-one, 2- (4-isopropylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) pentan-1-one, 2- (4-isobutylbenzyl) -2- ((N -Butyl) (methyl) amino]]-1- (4-morpholinophenyl) pentan-1-one, 2- (4-n-butyloxybenzyl) -2-[(n-butyl) (methyl) amino] -1- (4-morpholinophenyl) pentan-1-one, 2- (4-methylbenzyl) -2- [di (n-octyl) amino] -1- (4-morpholinophenyl) hexane-1 And 2- (4-n-dodecylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) octan-1-one and the like.
Among them, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one is preferable.

  When the aminoalkylphenone 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 varied from the forward taper to the reverse taper by varying the line taper angle described later on the cross-sectional shape of the black matrix. The forward tapered shape is a cross-sectional shape shown in FIG. 1 described later, and the reverse tapered shape is a cross-sectional shape shown in FIG. 2 described later.

For example, when the photopolymerization initiator (C) comprises only the oxime ester compound (C1) and the aminoalkylphenone photopolymerization initiator (C2), the amount of the aminoalkyl phenone photopolymerization initiator (C2) used is When the number is large, the values of θ shown in FIGS. 1 and 2 become large, and it is easy to form a patterned cured film whose cross-sectional shape is a reverse taper shape.
On the other hand, when the amount of use of the oxime ester compound (C1) is large, the values of each θ shown in FIGS. 1 and 2 become small, and it is easy to form a patterned cured film whose cross-sectional shape is a forward tapered shape.

This is because the aminoalkylphenone photopolymerization initiator (C2) tends to generate photopolymerization radicals relatively to the surface layer portion of the photosensitive composition (the surface facing the light to be exposed and the vicinity thereof). It is considered that the oxime ester compound (C1) tends to generate photopolymerization radicals relatively to the deep part of the photosensitive composition. This tendency is more pronounced as the film thickness of the photosensitive composition becomes thicker, but it is also recognized as a thin film thickness of 1 μm or less.
In addition, as a secondary effect of using an aminoalkylphenone photopolymerization initiator (C2) together with the oxime ester compound (C1), the sensitivity is comprehensively improved, and the cured product of the photosensitive composition is obtained with a small exposure amount. You can get it. Furthermore, when using an aminoalkylphenone photopolymerization initiator (C2) together with the oxime ester compound (C1), the straightness of the line edge and the adhesion to the substrate are good, and a black matrix with few pattern defects is formed. It's easy to do.

  When the photopolymerization initiator (C) contains an oxime ester compound (C1) and an aminoalkylphenone photopolymerization initiator (C2) in the photosensitive composition, the mass of the oxime ester compound (C1) and the amino 20 mass% or more and 75 mass% or less are preferable, and, as for the ratio of the mass of amino alkyl phenone type photo polymerization initiator (C2) to the total with the mass of alkyl phenone type photo polymerization initiator (C2), 25 mass% or more and 70 Mass% or less is more preferable, and 30 mass% or more and 60 mass% or less is particularly preferable. The oxime ester compound (C1) is selected such that the mixing ratio of the oxime ester compound (C1) in the case of forming a thick cured film is higher than the mixing ratio of the oxime ester compound (C1) in the case of forming a thin cured film. Is desirable to be incorporated into the photosensitive composition.

  Specific examples of the photopolymerization initiator other than the oxime ester compound (C1) and the aminoalkylphenone photopolymerization initiator (C2) that can be used as the photopolymerization initiator (C) include 1-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- (1 4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2 -Diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 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-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octa Methylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl)- 4,5-Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, 4,5-Triarylimidazole dimer, benzopheno 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3, 3- Dimethyl-4-methoxybenzophenone, benzyl, 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, p-tert-butylacetophenone, p-dime Luaminoacetophenone, p-tert-butyl trichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4 -Dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p -Methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2) -Yl) ethenyl] -4,6-bis (tric) Methyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n) -Butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triadidi , 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl And -s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators may be used alone or in combination of two or more, together with the oxime ester compound (C1).

（式（ｃ３）中、ＣＲは、下記式（ｃ３ａ）又は下記式（ｃ３ｂ）：

で表される基であり、Ｒ^ｃ１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい鎖状アルコキシ基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ２とＲ^ｃ３とは相互に結合して環を形成してもよく、Ｒ^ｃ４は１価の有機基であり、Ｒ^ｃ５は、水素原子、置換基を有してもよい炭素原子数１以上２０以下の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、ｎ１は０以上４以下の整数であり、ｎ２は０又は１である。）
で表される化合物である。
式（ｃ３）で表されるオキシムエステル化合物の合成や入手の容易性や、Ｒ^ｃ２及びＲ^ｃ３の選択により、オキシムエステル化合物の特性を調整しやすい点等から、式（ｃ３）中のＣＲとしては、式（ｃ３ａ）で表される基が好ましい。 The photosensitive composition also preferably contains an oxime ester compound (C3) together with the oxime ester compound (C1).
The oxime ester compound (C3) has the following formula (c3):

In the formula (c3), CR is a group represented by the following formula (c3a) or a group represented by the following formula (c3b):

R ^c1 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c2 and R ^c3 are respectively a chain alkyl group which may have a substituent, and a substituent R ^c2 and R ^c3 may be bonded to each other to form a ring; R ^c4 is a chain alkoxy group which may have, a cyclic organic group which may have a substituent, or a hydrogen atom; Is a monovalent organic group, and R ^c5 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent And n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1. )
It is a compound represented by
As the CR in the formula (c3), from the viewpoint that the properties of the oxime ester compound can be easily adjusted by the synthesis and availability of the oxime ester compound represented by the formula (c3) and the selection of R ^c2 and R ^c3 Is preferably a group represented by formula (c3a).

で示される構造中の＊で示される位置に結合するのが好ましい。Ｒ^ｃ１が複数である場合、複数のＲ^ｃ１は同一であっても異なっていてもよい。 In the group represented by the formula (c3a) or the formula (c3b) which is 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 bonded to the group represented by — (CO) _n2 — on the fused ring in the formula (c3a) or the 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 , synthesis of the compound represented by the formula (c 3) is easy, and so on, one of the one or more R ^c1 is Formula (c3a-1), and Formula (c3b-1):

It is preferable to bond to the position shown by * in the structure shown by When R ^c1 is plural, plural R ^c1 may be the same or different.

When R ^c1 is an organic group, R ^c1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples of R ^{c1 when it} is an organic group include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, saturated aliphatic acyloxy groups, alkoxycarbonyl groups, and substituents. A phenyl group which may be substituted, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy which may have a substituent Group, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, substituent A naphthoxycarbonyl group which may have, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, A heterocyclylcarbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group and the like can be mentioned.

When R ^c1 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c1 is an alkyl group, it may be linear or branched. Specific examples of R ^c1 being an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group etc. are mentioned. When R ^c1 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

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, and more preferably 1 or more and 6 or less. When R ^c1 is an alkoxy group, it may be linear or branched. When R ^c1 is an alkoxy group, specific examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, n Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c1 is an alkoxy group, the alkoxy group may contain 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, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

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, and more preferably 3 or more and 6 or less. When R ^c1 is a cycloalkyl group, specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of R ^c1 being a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. When R ^c1 is a saturated aliphatic acyl group, specific examples thereof include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Noyl group, and n-hexadecanoyl group etc. are mentioned. As specific examples in the case where R ^c1 is a saturated aliphatic acyloxy group, acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

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, and more preferably 2 or more and 7 or less. When R ^c1 is an alkoxycarbonyl group, specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples thereof include an isonononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. 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, and more preferably 11 or more and 14 or less. When R ^c1 is a phenylalkyl group, specific examples thereof include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in 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) ethyl group. . When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered single ring containing one or more of N, S and O, or such single rings or such single ring and benzene ring are condensed Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be either an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. Be When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^c1 is a heterocyclyl group.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and 7 to 20 carbon atoms which may have a substituent The following phenylalkyl groups, naphthyl groups which may have a substituent, naphthoyl groups which may have a substituent, naphthylalkyl groups having 11 to 20 carbon atoms which may have a substituent, and heterocyclyl And the like. Specific examples of these suitable organic groups are the same as R ^c1 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group.

When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^c1 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms And a monoalkylamino group having the formula, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 or more and 4 or less is preferable. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c1 is preferably a nitro group or a group represented by R ^c6- CO-, since the sensitivity tends to be improved. R ^c6 is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of preferable groups as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent And heterocyclyl groups which may be mentioned. Among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable as R ^c6 .

In formula (c3a), R ^c2 and R ^c3 each represent a chain-like alkyl group which may have a substituent, a chain-like alkoxy group which may have a substituent, or a ring which may have a substituent It is an organic group or a hydrogen atom. R ^c2 and R ^c3 may be bonded to each other to form a ring. Among these groups, as R ^c2 and R ^c3 , chain-like alkyl groups which may have a substituent are preferable. When R ^c2 and R ^c3 are a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.

When R ^c2 and R ^c3 are a chained alkyl group having no substituent, the number of carbon atoms in the chained alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. preferable. When R ^c2 and R ^c3 are a chain alkyl group, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. , N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Groups, isononyl groups, n-decyl groups, isodecyl groups and the like. In addition, when R ^c2 and R ^c3 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^c2 and R ^c3 are a chained alkyl group having a substituent, the number of carbon atoms of the chained alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less . In this case, the number of carbon atoms 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 substituent which the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, fluorine atom, chlorine atom and bromine atom are preferable. The cyclic organic group includes a cycloalkyl group, an aromatic hydrocarbon group and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples where R ^c1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples where R ^c1 is a heterocyclyl group. When R ^c1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1 or more and 10 or less are preferable, and, as for the carbon atom number of the alkoxy group contained in the alkoxycarbonyl group, 1 or more and 6 or less are more preferable.

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

When R ^c2 and R ^c3 are 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 1 or more and 6 or less. preferable. When R ^c2 and R ^c3 are a chain alkoxy group, specific examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, tert. -Butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, A sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, an isodecyloxy group and the like can be mentioned. When R ^c2 and R ^c3 are an alkoxy group, the alkoxy group may contain 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, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.
When R ^c2 and R ^c3 are a chained alkoxy group having a substituent, the substituent which the alkoxy group may have is the same as 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 cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups and heterocyclyl groups. When R ^c2 and R ^c3 are cyclic organic groups, the substituents which the cyclic organic group may have are the same as in the case where R ^c2 and R ^c3 are chain alkyl groups.

When R ^c2 and R ^c3 are an aromatic hydrocarbon group, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? And a plurality of benzene rings is preferably a group formed by condensation. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is especially preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

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

When R ^c2 and R ^c3 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered single ring containing one or more of N, S and O, or such single rings or such single ring and benzene ring And a fused heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be either an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. Be

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

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

Examples of preferable groups among R ^c2 and R ^c3 described above include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and 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 in a straight chain alkylene group A ¹ is preferably 1 to 10, 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1 or more and 10 or less are preferable, and, as for the carbon atom number of an alkoxy group, 1 or more and 6 or less are more preferable. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When 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, and 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. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^c2 and R ^c3 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group which R ^c2 and R ^c3 have as a substituent.

Preferred specific examples of R ^c2 and R ^c3 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n group - Cyanoalkyl groups such as ethyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl and 8-cyano-n-octyl; 2-phenylethyl, 3-phenyl-n-propyl Phenylalkyl such as 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl and 8-phenyl-n-octyl Group: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- group Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopenty Cycloalkylalkyl groups such as: n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-Methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n Pentyl group, 6-ethoxycarbonyl n-hexyl group, 7-ethoxy Alkoxycarbonylalkyl groups such as rubynyl-n-heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro group -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro And propyl alkyl and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

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

Examples of suitable organic groups of R ^c4 are, like R ^c1 , alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent A benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl which may have a substituent Group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ^c1 . Further, R ^c4 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 substituent which the phenylthioalkyl group may have are the same as the substituents which the phenyl group contained in R ^c1 may have.

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

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

When A ³ is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A ³ is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Preferred examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, and 7 or more carbon atoms 20 or less aralkyl groups, and an aromatic hydrocarbon group having 6 to 20 carbon atoms can be mentioned. Specific preferable examples of A ⁴ is methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl Groups, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferable specific examples of the group represented by -A ³ -CO-O-A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxy carboni -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

（式（ｃ３−ａ）及び（ｃ３−ｂ）中、Ｒ^ｃ７及びＲ^ｃ８はそれぞれ有機基であり、ｎ３は０以上４以下の整数であり、Ｒ^ｃ７及びＲ^ｃ８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ７とＲ^ｃ８とが互いに結合して環を形成してもよく、ｎ４は１以上８以下の整数であり、ｎ５は１以上５以下の整数であり、ｎ６は０以上（ｎ５＋３）以下の整数であり、Ｒ^ｃ９は有機基である。） As mentioned above, although ^demonstrated about R ^c4, as R ^c4 , the group represented by a following formula (c3-a) or (c3-b) is preferable.

(In the formulas (c3-a) and (c3-b), R ^c7 and R ^c8 are each an organic group, n 3 is an integer of 0 or more and 4 or less, and R ^c7 and R ^c8 are adjacent on the benzene ring When present at the position, R ^c7 and R ^c8 may combine with each other to form a ring, n4 is an integer of 1 to 8; n5 is an integer of 1 to 5; n6 is 0 More than (n5 + 3) is an integer less than, and ^Rc9 is an organic group.

Examples of the organic group for R ^c7 and R ^c8 in the formula (c3-a) are the same as R ^c1 . As R ^c7 , an alkyl group or a phenyl group is preferable. 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, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R ^c7 is most preferably a methyl group. When R ^c7 and R ^c8 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (c3-a), in which R ^c7 and R ^c8 form a ring, include naphthalene-1-yl group, And 4-tetrahydronaphthalen-5-yl and the like. In the above formula (c3-a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (c3-b), R ^c9 is an organic group. As the organic group, the same groups as the organic groups described for R ^c1 can be mentioned. Of the organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The carbon atom number of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. Preferred examples of R ^c9 include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Among these, a methyl group is more preferable.

  In said formula (c3-b), n5 is an integer of 1 or more and 5 or less, an integer of 1 or more and 3 or less is preferable, and 1 or 2 is more preferable. In the above formula (c3-b), n6 is 0 or more (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 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (c3), R ^c5 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent which may be possessed when R ^c5 is an aliphatic hydrocarbon group include a phenyl group and a naphthyl group. Moreover, as a substituent which may be possessed when R ^c1 is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In formula (c3), R ^c5 represents a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-cyclopentylethyl group, 2-cyclobutylethyl group, cyclohexylmethyl group, A phenyl group, a benzyl group, a methylphenyl group, a naphthyl group etc. are illustrated preferably, Among these, a methyl group or a phenyl group is more preferable.

Preferred specific examples of the compound represented by the formula (c3) include the following compounds.

  The content of the photopolymerization initiator (C) in the photosensitive composition is not particularly limited as long as the object of the present invention is not impaired. The content of the photopolymerization initiator (C) is preferably 0.1% by mass to 50% by mass, and more preferably 0.3% by mass to 30% by mass, with respect to the mass of the solid content of the photosensitive composition. Particularly preferred is 0.5% by mass or more and 20% by mass or less. By using the photopolymerization initiator (C), by using the photopolymerization initiator (C) in an amount within this range, the mechanical properties, solvent resistance, chemical resistance, etc. of the cured product are not impaired. It is easy to obtain the desired effect.

<Shading agent (D)>
The photosensitive composition contains a light shielding agent (D). The light shielding agent (D) essentially contains a resin-coated carbon black (D1). For this reason, it is easy to form the cured film which is excellent in both light-shielding property and insulation using a photosensitive composition.

The uncoated carbon black not coated with a resin, which is an object of the coating with a resin, is not particularly limited, and various carbon blacks conventionally used as a light shielding agent can be used. Specifically, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used as the uncoated carbon black.
The uncoated carbon black may be used alone or in combination of two or more.

  As uncoated carbon black, carbon black which has been treated to introduce an acidic group is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity as defined by Bronsted. A carboxy group, a sulfonic acid group, a phosphoric acid group etc. are mentioned as a specific example of an acidic group. The acidic group introduced into carbon black may form a salt. The cation which forms a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ions are preferable.

  Among the carbon blacks subjected to the treatment for introducing the acidic group described above, from the viewpoint of achieving high resistance of the light-shielding cured film formed using the photosensitive composition, a carboxylic acid group, a carboxylic acid group Preferred are carbon blacks having one or more functional groups selected from the group consisting of sulfonic acid groups, and sulfonic acid groups.

The method for introducing an acidic group into carbon black is not particularly limited. As a method of introduce | transducing an acidic group, the following method is 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, hydrogen sulfite or the like.
2) A method of diazo coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group, and a carbon black having a hydroxyl group by a Williamson etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method in which a Friedel-Crafts reaction is performed on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group, followed by deprotection.

  Among these methods, method 2) is preferred because the introduction treatment of the acid group is easy and safe. As an organic compound which has an amino group and an acidic group used by the method 2), the compound which the amino group and the acidic group couple | bonded with the aromatic group is preferable. Examples of such compounds include aminobenzene sulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

  The number of moles of the acidic group introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of the acidic group introduced into 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 the resin is not particularly limited.
Examples of the coating method include a method of removing the solvent from the coating layer after coating the carbon black particles with a solution of resin, a dispersion containing fine particles of resin, or an emulsion.
In addition, in the case of coating with a curable resin, after attaching a monomer or an uncured resin precursor to the surface of carbon black particles, the monomer is polymerized or an uncured resin precursor May be cured. In this case, the monomer or uncured resin precursor is attached to the surface of the carbon black particles by coating the carbon black particles with a solution of the monomer or uncured resin precursor. It is damn good. Furthermore, as required, a polymerization initiator and a curing agent may be used for both the monomer and the uncured resin precursor.

  It is also possible to produce a resin-coated carbon black resin (D1) by dispersing carbon black particles in a matrix made of resin and then finely pulverizing the resin containing carbon black particles.

  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 electric resistivity as dry powder of the resin-coated carbon black (D1), that is, so-called 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 resins that can be used to coat carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, poly Thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfo polyphenylene sulfone, poly arylate, polyether ether ketone and the like can be mentioned. Among these, epoxy resins are particularly preferably used.

The form of the light shielding agent (D) such as the resin-coated carbon black (D1) used for preparation of the photosensitive composition is not particularly limited. The light shielding agent (D) may be used as a powder or may be used as a dispersion. The light shielding agent (D) is preferably used as a dispersion to prepare a photosensitive composition.
A dispersion containing two or more light shielding agents may be used as the dispersion. In addition, two or more types of dispersions may be used, each containing a different type of light shielding agent.

  The light shielding agent (D) containing the resin-coated carbon black (D1) is preferably used as a dispersion dispersed in a dispersion medium as described above. Examples of the dispersion medium include organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate 3-ethoxyethyl propionate, and propylene glycol monomethyl ether propionate. Or water can be used.

Even if a dispersant is added to the light shielding agent (D) in order to stabilize the dispersion of the light shielding agent (D) in the dispersion liquid and to improve the dispersibility of the light shielding agent (D) in the photosensitive composition. Good.
As a dispersing agent, it is preferable to use a polyethyleneimine type, a urethane resin type, and an acrylic resin type polymer dispersing agent. Since the light shielding agent (D) contains a resin-coated carbon black (D1), an acrylic resin-based dispersant or a urethane resin-based dispersant which is suitably used for dispersing carbon black may be used as the dispersant. preferable.
In addition, the corrosive gas resulting from a dispersing agent may arise from a cured film. For this reason, it is also an example of a preferred embodiment that the light shielding agent (D) is subjected to 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 measured at 25 ° C. using a cone-plate viscometer. If the viscosity is in this range, there is no restriction on the compounding ratio of the resin-coated carbon black and the dispersion medium, and the resin-coated carbon black content depends on the kind of the dispersion medium. An example is 1% by mass or more and 50% by mass or less.

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

  When a photosensitive composition contains resin-coated carbon black (D1) as a light shielding agent (D), a cured film with high volume resistivity can be formed using a photosensitive composition. For this reason, it is easy to form a cured film having a high unit optical density while avoiding a significant decrease in the insulation of the cured film due to an increase in carbon black.

On the other hand, in general, when forming a cured film having a high unit optical density using a photosensitive composition, when exposing a coating film made of the photosensitive composition, curing in the deep portion of the coating film is insufficient. It is easy to become. However, when the photosensitive composition contains the above-mentioned oxime ester compound (C1) as a photopolymerization initiator (C), it is easy to sufficiently cure the deep portion of the coated film, and a cured film having good adhesion to the substrate Easy to form. At the same time, this has the effect of making the cross section of the black matrix pattern made of the cured photosensitive composition forward-tapered, and when a cured product of the photosensitive composition is used to construct a liquid crystal display panel or a liquid crystal display device. The light bleeding at the pattern end can be reduced (to be described in detail later).
In addition, if the deep portion of the coating film is sufficiently cured, the durability of the cured film in a high temperature, high humidity, and high pressure environment is improved, and water is contained inside the cured film even if the cured film is exposed to such a harsh environment. It is difficult to infiltrate, and the adhesion of the cured film to the substrate and the volume resistivity (high insulation) are not easily impaired.

  In addition, with the realization of a high unit optical density, it is easy to reduce the thickness of the black matrix made of the cured product of the photosensitive composition. When a thin black matrix is used, light bleeding at the pattern end face of the black matrix in the liquid crystal display can be further reduced, and the material cost can also be further reduced.

  The photosensitive composition may contain, as a light shielding agent (D), a light shielding agent other than the resin-coated carbon black (D1), in addition to the resin-coated carbon black (D1). When the photosensitive composition contains another light shielding agent, the mass ratio 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 80 mass% or more is further more preferable, 90 mass% or more is especially preferable, and 95 mass% or more is the most preferable.

  Other light shielding agents that can be used together with resin-coated carbon black include uncoated carbon black, lactam pigments, fine particles containing silver tin (AgSn) alloy as a main component, titanium black, copper, iron, manganese, cobalt, chromium And various pigments such as nickel, zinc, calcium, silver and the like, metal oxides such as complex oxides, metal sulfides, metal sulfates or metal carbonates, regardless of organic or inorganic substances.

In the photosensitive composition, as the light shielding agent (D), a pigment such as resin-coated carbon black (D1) may be used in combination with a dye. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the photosensitive composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes and the like. be able to.
Further, these dyes can be dispersed in an organic solvent or the like by lake formation (salt formation) and used as a light shielding agent (D).
Besides these dyes, for example, those disclosed in JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. The dyes described above can also be preferably used.

The total content of the light shielding agent (D) in the photosensitive composition can be appropriately selected as long as the object of the present invention is not impaired. Typically, 90 mass% of the total mass of the solid content of the resin composition % Or less is preferable, 2 mass% or more and 85 mass% or less is preferable, and 3 mass% or more and 80 mass% or less is more preferable. The upper limit of the total content of the light shielding agent (D) relative to the mass of the total solid content of the photosensitive composition is 90, as long as a cured film having a sufficiently high light shielding property can be formed using the photosensitive composition. It may be not more than mass%, may be not more than 85% by mass, and may be not more than 80% by mass.
In the present specification, the amount of the above-mentioned light shielding agent (D) can be defined as a value including the amount of the dispersing agent present together with the light shielding agent (D).

<Other ingredients (E)>
Hereinafter, as other components, optional components will be described below. It does not restrict | limit in particular about the addition amount of another component (E). Other components (E) can be used in amounts that do not inhibit the object of the present invention.

(Surface modifier)
The surface conditioner reduces the surface tension of the photosensitive composition, thereby suppressing the occurrence of surface defects and appearance defects (non-uniform distribution of pigments) caused by non-uniform distribution of pigments. Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified with an aralkyl group or a polyester chain, and the like can be suitably used.

(Adhesion improver)
Well-known coupling agents, such as a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, can be used. Among these, a silane coupling agent can be used suitably from a viewpoint of improving adhesiveness with a glass substrate.

  The photosensitive composition may contain various additives other than the above, as necessary. Specifically, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersion aid, a filler, an antioxidant, an ultraviolet light absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, Surfactants, chain transfer agents, photoinitiator aids, solvents and the like are exemplified. Any of the additives known in the art can be used.

As surfactant, an anionic compound, a cationic compound, a nonionic compound etc. are mentioned, for example.
Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether.
As an antifoamer, a silicone type compound, a fluorine type compound, etc. are mentioned, for example.
As a chain transfer agent, a mercaptan type-compound, a halogen type compound, a quinone type compound, the (alpha)-methylstyrene dimer etc. are mentioned, for example. By containing a chain transfer agent, pattern shape (especially, CD change of hole pattern, exposure margin) can be controlled well. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable in that it can reduce sublimation, coloring and odor in addition to the above effects.
As a photoinitiator adjuvant, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10 And -dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiators may be used alone or in combination of two or more.

<Solvent (S)>
The photosensitive composition preferably contains a solvent (S) for dilution. As the solvent (S), for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, di (Poly) alkylene glycol monoalkyl ethers such as ropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as 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; Ethers, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl lactates; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, acetic acid n-propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Ethyl esters, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; toluene, aromatic hydrocarbons such as xylene; N-methylpyrrolidone, N, N-dimethyl Amides such as formamide, N, N-dimethylacetamide and the like can be mentioned. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (MEDG), cyclohexanone, 3-methoxybutyl acetate (MBA) is preferable because it exhibits excellent solubility in the above-mentioned photopolymerization initiator (C), and it is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.
The content of the solvent (S) is preferably such that the solid content concentration of the photosensitive composition is from 1% by mass to 50% by mass, and more preferably from 5% by mass to 40% by mass.

«Method of preparing photosensitive composition»
The photosensitive composition is prepared by uniformly stirring, mixing, and uniformly dissolving and dispersing the above-mentioned components. The mixing may be performed by a stirrer such as a roll mill, a ball mill, or a sand mill. It can be prepared by filtration through a filter such as a 2 μm membrane filter, if necessary.

«Cured product formation method and cured product»
The cured product forming method is the same as the conventional cured product forming method using the photosensitive composition, except for using the above-described photosensitive composition.

  The method for forming a cured product using the above-described photosensitive composition is not particularly limited, and can be appropriately selected from conventionally used methods. The cured product is formed as a molded product of a desired shape by control of the shape of the coating film upon application of the photosensitive composition, or by combination of regioselective exposure and development. As a suitable method for forming a cured product, a method including a coating film forming step of forming a coating film using the above-mentioned photosensitive composition, and an exposure step of exposing the above-mentioned coating film is mentioned. When the exposure is carried out position selective, the exposed coating may be developed with a developer to obtain a patterned cured product.

First, in the coating film forming step, for example, a contact transfer type coating apparatus such as a roll coater, a reverse coater or a bar coater, a spinner (rotary coating apparatus), a curtain flow coater or the like on a substrate on which a cured product is to be formed. The above-described photosensitive composition is applied using a non-contact application device, and the solvent is removed by drying (pre-baking) to form a coating film, if necessary.
In addition, a droplet coated on a substrate, a photosensitive composition embedded in a recess of a substrate having unevenness, a photosensitive composition filled in a recess of a mold, and the like are also referred to as “coating film” for convenience. .

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

Next, the formed coating is subjected to an exposure step. In the exposure step, ArF excimer laser coating, KrF excimer laser, _{F 2} excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beams, X-rays, soft X-ray, i-ray, g-line, h-line Etc. by irradiating a radiation or electromagnetic wave such as. Exposure to the coating may be performed positionally selective through a negative mask. Exposure dose varies depending on the composition of the photosensitive composition, preferably for example, about 10 mJ / cm ² or more 600 mJ / cm ² or less.

The exposed coating is developed as needed.
The photosensitive composition described above is unlikely to be excessively dissolved in an alkali developer after exposure. For this reason, by using the above-mentioned photosensitive composition, it is easy to form a patterned cured product of a good shape in which the exposed area is a convex area and the unexposed area is a concave area.

  In the development step, the exposed coating film is developed with a developer to form a cured product patterned in a desired shape. The development method is not particularly limited, and an immersion 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, quaternary ammonium salts and the like.

  Then, if necessary, the cured product after exposure or the patterned cured product after development may be post-baked to further promote heat curing. The post-baking temperature is preferably 150 ° C. or more and 270 ° C. or less.

  The cured product is formed using the photosensitive composition described above. The application of the cured product is not particularly limited. The cured product is particularly preferably used as a black matrix used in various color filters for image display devices. The color filter provided with the black matrix which consists of hardened | cured material formed using the above-mentioned photosensitive composition is used suitably for an image display panel. Such an image display panel is suitably used in various image display devices such as a liquid crystal display device, an organic EL display device, an inorganic EL display device, and the like. Further, it is also suitably used in a touch panel having both an image display panel and a surface sensor composed of a capacitance electrode, a resistance electrode and the like.

«Color filter and image display panel»
Hereinafter, an example of the image display panel 1 provided with 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 type image display panel 1 which displays an image by driving a liquid crystal which is a representative example of the image display panel 1.
In the image display panel 1, the polarizing layer 50b, the TFT (thin film transistor) supporting substrate 90b, the liquid crystal layer 30, the color filter 100, the CF (color filter) supporting substrate 90a, and the polarizing layer 50b are in this order It is stacked.
In the liquid crystal layer 30, spacers for making the layer thickness of the liquid crystal layer 30 constant are provided at predetermined intervals in the in-plane direction (not shown).

The polarization layer 50a and the polarization layer 50b are arranged to form a predetermined polarization angle. Further, a backlight device is provided on the side of the image display panel 1 on which the polarizing layer 50b is provided (not shown).
The CF support substrate 90 a and the TFT support substrate 90 b are each made of a translucent material such as glass or a transparent resin in order to transmit light emitted from the backlight device.

The color filter 100 is supported by the CF support substrate 90 a on the liquid crystal layer 30 side of the CF support substrate 90 a. The color filter 100 is composed of a light shielding layer 10 and colored layers 20a, 20b and 20c. The light shielding layer 10 corresponds to a black matrix.
The hues of the colored layers 20a, 20b, and 20c are not black, and are typically chromatic colors such as red (R), green (G), and blue (B).
The colored layers 20a, 20b, and 20c are a first colored layer 20a, a second colored layer 20b, and a third colored layer 20c that transmit light of different hues. The hues 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).
Wirings 40 are formed on the surface of the TFT support substrate 90 b on the liquid crystal layer 30 side. A well-known TFT substrate can be used as the TFT support substrate 90b.

  The light shielding layer 10 is made of a cured product of the photosensitive composition described above. Therefore, the light shielding layer 10 exhibits a desired high unit optical density. Further, as shown in FIG. 1 described later, the cross-sectional shape of the light shielding layer 10 is a forward taper with respect to the support substrate 90 a.

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

[Examples 1 to 3 and Comparative Examples 1 to 5]
Alkali-soluble resin (A-1), photopolymerizable monomer (B-1), photopolymerization initiators (C-1, C-2, C-3, and C-4), light shielding agent (D-1) , And D-2), and additives (E-1 and E-2) in the proportions described in Table 1, respectively, a mixture of organic solvents (S-1, S-2 and S-3) The photosensitive composition was prepared by dispersing and dissolving in a solvent). The mixing ratio of each of the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, the light shielding agent and the additive, which is a solid content, is as shown in Table 1 by mass. Moreover, the organic solvent was prepared so that solid content concentration in a photosensitive composition might be 15 mass%.

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

Preparation Example 1
In a 500 mL four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid are charged. It was dissolved by heating to 90 ° C. or more and 100 ° C. or less while blowing air at a rate of 25 mL / min. Next, the solution was gradually heated while keeping the solution cloudy, and was completely dissolved by heating to 120 ° C. At this time, the solution gradually became clear and viscous, but stirring was continued. During this time, the acid value was measured, and heating and stirring were continued until it was less than 1.0 mg KOH / g. It took 12 hours for the acid value to reach the target value. Then, the reaction solution was cooled to room temperature to obtain a colorless and colorless solid epoxy resin of bisphenol fluorene type represented by the following formula.

  Subsequently, 600 g of 3-methoxybutyl acetate is added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, and then 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide are dissolved. The mixture was mixed, heated gradually, and reacted at 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 is mixed and reacted at 90 ° C. for 6 hours to obtain a resin (R-1) which is a cardo resin. The The disappearance of the acid anhydride group was confirmed by IR spectrum.

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

The following P-1, P-2, P-3, and P-4 were used as a photoinitiator (C-1).

Moreover, as a light shielding agent (D), the light shielding agent D-1 and the light shielding agent D-2 which are dispersion liquid of a light shielding agent, respectively were used.
The light shielding agent D-1 is an epoxy resin-coated carbon black dispersion (the dispersion medium is propylene glycol monomethyl ether acetate (PM)). For the light shielding agent D-1, the dispersion average particle size of the resin-coated carbon black is 130 nm, and the powder resistance is 5 Ω · cm. The light shielding agent D-2 is a carbon black dispersion without resin coating (the dispersion medium is propylene glycol monomethyl ether acetate (PM)). For the light-shielding agent D-2, the dispersion average particle size of carbon black is 110 nm, and the powder resistance is 1.0 × 10 ⁻⁶ Ω · cm, which is the lower measurement limit. In addition, in Table 1, about description of the weight part of light-shielding agent D-1 and D-2, it describes by the weight of each solid content.

  As an additive E-1, BYK-310 (made by Bick Chemie Japan KK) which consists of polyester modified polydimethylsiloxane which is a surface conditioner was used. As the additive E-2, 3-phenylamino-n-propyl (trimethoxy) silane, which is an adhesion improver, was used.

The following S-1, S-2, and S-3 were mixed as a solvent, and it used as mixed solvent. The mixing ratio (weight ratio) of each is 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 which the above-mentioned light-shielding agent D-1 and D-2 have.

  Using the photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 5, the cured product of the photosensitive composition was evaluated according to the following preparation method and measurement method.

<Creation of Substrate Cg Having Cured Film>
The photosensitive composition obtained in each Example and Comparative Example is applied on a glass substrate of 100 × 100 mm and 0.7 mm thickness using a spin coater, and then the coating film is prebaked at 90 ° C. for 60 seconds to obtain a film thickness A cured film of 1.2 μm was obtained.
Next, using the exposure apparatus TME150RTO (manufactured by Topcon), the coating film was exposed on the entire surface at an exposure amount of 40 mJ / cm ² without using a mask (ultraviolet exposure by an ultrahigh pressure mercury lamp).
After exposure, development was performed at 25 ° C. for 60 seconds using an aqueous solution of potassium hydroxide having a concentration of 0.05% by mass as a developer.
The exposed coated film after development was post-baked at 230 ° C. for 30 + 180 minutes (total 210 minutes) to obtain a substrate Cg.

<Measurement of unit optical density>
For the substrate Cg, the optical density of the cured film was measured using an optical density measurement device D-200 II (manufactured by Gretag Macbeth), and the unit optical density (unit: / μm) was determined by film thickness conversion. The results are set forth in Table 2.

<Measurement of adhesion>
A 1 mm wide grid-like cut (cross cut) was made in the cured film in the substrate Cg.
Subsequently, a PCT test (pressure cooker test) was carried out for 36 hours under an environment of 120 ° C., 100% humidity and 2 atm.
Thereafter, the temperature was returned to room temperature, and a tape peeling test defined in ASTM-D3359-09e2 was performed to observe the peeling of each grid. The results of the tape peeling test were evaluated according to the following criteria. The results are set forth in Table 2.
◎ (Rank 5B): There was no peeling at all.
○ (Rank 4B): The ratio of the number of peeled cured films to the total number of cured films divided by the grid-like incision was 5% or less.
Δ (Rank 3 B): The ratio of the number of peeled cured films to the total number of cured films divided by lattice cutting was more than 5% and 15% or less. Peeling was over 15%.
X (Rank 2 B to 0 B): The ratio of the number of peeled cured films to the total number of cured films divided by lattice cutting was 15% or more.

<Preparation of Substrate Cs Having Cured Film>
Instead of the glass substrate, a 5-inch low resistance silicon wafer (surface resistance: 0.01 to 0.03 Ω) was used. Substrate Cs provided with a cured film of a photosensitive composition was obtained using the photosensitive composition obtained in each example and comparative example by the same preparation method as substrate Cg.

<Measurement of volume resistance>
The substrate Cs was subjected to a PCT test in which it was exposed to an environment of 120 ° C., 100% humidity and 2 atm for 1 hour. Thereafter, the temperature is returned to room temperature, and the volume resistance value of the cured film is calculated using a resistivity meter Hiresta MCP HT-450 (manufactured by Mitsubishi Chemical) according to JIS-K6911 (measurement conditions: voltage 10 V, 60 seconds). The results are set forth 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.

<Creation of a substrate Pg provided with a patterned cured film>
The photosensitive composition obtained in each Example and Comparative Example is applied on a glass substrate of 100 × 100 mm and 0.7 mm thickness using a spin coater, and then the coating film is prebaked at 90 ° C. for 60 seconds to obtain a film thickness A cured film of 1.2 μm was obtained.
Next, using a light exposure apparatus (manufactured by Topcon TME150RTO), the coating film was exposed at a dose of 40 mJ / cm ² through a photomask having a 10 μm line and space pattern (by an ultra-high pressure mercury lamp UV exposure).
After exposure, development was performed at 25 ° C. for 60 seconds using an aqueous solution of potassium hydroxide having a concentration of 0.05% by mass as a developer.
The exposed coating 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 taper angle)>
The line and space pattern formed on the substrate Pg is observed with a scanning electron microscope S-9220 (manufactured by Hitachi, Ltd.), and any of Examples 1 to 3 and Comparative Examples 1 to 5 can form a line and space pattern. It was confirmed that each photosensitive composition was a negative type photosensitive composition having a sensitivity to cure at an exposure dose of 40 mJ / cm 2 or less.
Then, in more detail, the pattern peeling defect, line straightness (mask fidelity), and line taper angle were evaluated.
The pattern peeling defect was evaluated according to the following criteria based on the observation result of 10 lines.
○: There was no pattern peeling.
Fair: Of 10 lines, the number of lines in which peeling was observed was 1 or 2.
X: Of 10 lines, the number of lines in which peeling was observed was 3 to 10.
The straightness of the line was evaluated according to the following criteria.
○: Straight pattern was formed ○
X: Defects such as distortion, meandering, and missing edges were observed.

As for the line taper angle, the angle θ between the substrate 90a and the side surface of the line portion 10 was measured as shown in FIG. In the case of a trapezoidal shape as shown in FIG. 1, θ is more than 0 ° and less than 90 °, and is called a forward taper. Further, in the case of the inverted trapezoidal shape as shown in FIG. 2, θ is more than 90 degrees and less than 180 degrees, and is called an inverse taper. The line taper angle (pattern cross-sectional shape) was evaluated according to the following criteria.
A: measurement angle θ is 70 degrees or more and 85 degrees or less ○: measurement angle θ is 86 degrees or more and 90 degrees or less Δ: measurement angle θ is 91 degrees or more and 100 degrees or less x: measurement angle 100 degrees or more In FIG. 2, the contact surface of the substrate 90 a and the line portion 10 of the cured photosensitive composition pattern is used as a reference surface, and the angle between the parallel line of the reference surface and the line side surface is expressed as θ. It is the same.

<Line taper angle θ required for liquid crystal display panel>
Here, the line taper angle θ is supplemented. The line taper angle θ is desirably 90 degrees in order to secure the fidelity to the mask pattern. However, when a black matrix using a photosensitive composition is incorporated into an image display panel, liquid crystal may be disposed in contact with the black matrix.
The molecular orientation of the liquid crystal is controlled by voltage, and in the optical system including the polarizing plate, display of characters, images and the like is performed by dramatically changing the light transmittance. When the liquid crystal is disposed in contact with the black matrix, the liquid crystal alignment behavior is different from that of the flat portion (corresponding to the line portion or the space portion described above) at the pattern boundary portion of the black matrix under the influence of the boundary step. Show the behavior. As an optical phenomenon, even if the light transmittance is 0% at the flat pattern portion, the light beam is transmitted at the pattern boundary portion, and it is observed as light bleeding or light leakage at the pattern boundary portion, and the image display Not suitable for panels and image display devices.
The light bleeding phenomenon is remarkable when the line taper angle θ of the black matrix pattern is more than 90 degrees, and is reduced when the line taper angle θ is 90 degrees or less. When a drive test is performed as the image display panel and the image display device, the line taper angle θ of 85 degrees or less is an appropriate angle. If the angle is less than 70 degrees, the light transmission area narrows (corresponding to narrowing of the space other than the line 10 in FIG. 1), and the light amount decreases, so it is not suitable as an image display panel or an image display device.
Therefore, as the liquid crystal display panel and the liquid crystal display device, the line taper angle θ is preferably 90 degrees or less, and most preferably 70 degrees or more and 85 degrees or less.

*１ 120℃・2気圧・36時間処理後
*２ 120℃・2気圧・1時間処理後

* 1 After processing at 120 ° C · 2 atm · 36 hours
* 2 After 120 ° C · 2 atm · 1 hour treatment

According to Tables 1 and 2, a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D), wherein the photopolymerization initiation is carried out When using the photosensitive compositions of Examples 1 to 3 which contain the oxime ester compound (C1) having a predetermined structure as the curing agent (C) and the resin-coated carbon black (D1) as the light shielding agent (D) Adhesion to a good substrate while having optical density (3.8 / μm) and high volume resistivity (1.0 × 10 ¹³ Ω · m or more, more preferably 1.0 × 10 ¹⁴ Ω · m or more) It can be seen that it is possible to form a patterned cured film having good properties and a good pattern shape (defect, straightness, line taper angle θ).

  On the other hand, when using the photosensitive composition of Comparative Examples 1 to 4 which does not contain the compound corresponding to the oxime ester compound (C1), adhesion to the substrate, volume resistivity, and pattern shape (defects, straightness, taper angle It can be seen that only cured films with insufficient θ) can be formed.

DESCRIPTION OF SYMBOLS 1 image display panel 10 light-shielding layer 20a, 20b, 20c coloring layer 30 liquid crystal layer 40 wiring 50a, 50b polarization layer 90a CF support substrate 90b TFT support substrate 100 color filter

Claims (12)

A photosensitive composition comprising an alkali soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D),
The photopolymerization initiator (C) has the following formula (c1):

(In formula (c1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent, or a heterocyclyl group which may have a substituent, R ³ is a monovalent organic group, R ⁴ is a monovalent organic group, and R ⁵ and R ⁶ each independently have a benzene ring which may have a substituent, or a substituent Naphthalene ring, and m1, m2 and m3 are each 0 or 1)
Containing an oxime ester compound (C1) represented by
The said oxime ester compound (C1) is the following (1)-(3):
(1) R ¹ includes a group represented by —OR ⁷ , R ⁷ is a halogenoalkyl group (2) m 2 is 1 and R ⁴ includes a group represented by —OR ⁷ , R ⁷ At least one of the following conditions: is a halogenoalkyl group (3) R ³ is a branched alkyl group which may have a substituent, and
The photosensitive composition in which the said light-shielding agent (D) contains resin-coated carbon black (D1). The oxime ester compound (C1) has the following formula (c1-III):

(In the formula (c1-III), R ¹ , R ² , R ³ , R ⁴ , m 1, m 2 and m 3 are the same as the formula (c 1).)
The photosensitive composition of Claim 1 which is a compound represented by these.   The photosensitive composition of Claim 1 or 2 in which the said photoinitiator (C) further contains an aminoalkyl phenone compound (C2).   The photosensitive composition according to any one of claims 1 to 3, wherein the resin-coated carbon black (D1) contains an epoxy resin-coated carbon black (D1).   The content of the said photoinitiator (C) is 1 mass% or more and 15 mass% or less with respect to the mass of solid content of the said photosensitive composition, The any one of Claims 1-4 Photosensitive composition.   The photosensitive composition according to any one of claims 1 to 5, wherein the content of the oxime ester compound (C1) relative to the mass of the photopolymerization initiator (C) is 30% by mass or more.   A cured product of the photosensitive composition according to any one of claims 1 to 6.   A color filter comprising a black matrix comprising the cured product according to claim 7.   An image display panel comprising the color filter according to claim 8.   An image display apparatus comprising the image display panel according to claim 9. Applying the photosensitive composition according to any one of claims 1 to 6 on a substrate to form a coating film;
Position-selectively exposing the coating film;
Developing the exposed coating film;
A method of producing a patterned cured film comprising: The method according to claim 11, wherein the patterned cured film is a black matrix.

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