JP6832168B2 - Resin composition, black matrix, display device, and method for manufacturing black matrix - Google Patents

Description

The present invention relates to a resin composition, a black matrix obtained by curing the resin composition, a display device including the black matrix, and a method for producing a black matrix using the above-mentioned resin composition.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes are formed so as to face each other. A color filter having pixels of each color such as red (R), green (G), and blue (B) is formed inside one of the substrates. Then, in this color filter, in order to prevent color mixing of different colors in each pixel and to hide the electrode pattern, usually, the pixels of each of R, G, and B are arranged in a matrix so as to partition them. A black matrix is formed.

Generally, color filters are formed by lithographic methods. Specifically, first, a black photosensitive composition is applied, exposed, and developed on a substrate to form a black matrix. Then, for each of the photosensitive compositions of each color of red (R), green (G), and blue (B), coating, exposure, and development are repeated to form a pattern of each color at a predetermined position to form a color filter. Form.

As a method for forming a colored film constituting a color filter, for example, a method for forming a black matrix, a method using a negative type photosensitive resin composition has been proposed.
For example, Patent Document 1 includes a resin having a cardo structure and an acrylic resin as an alkali-soluble resin as a black photosensitive resin composition capable of forming a black matrix having excellent adhesion to a substrate and light-shielding property. A negative type photosensitive resin composition is shown.

Japanese Unexamined Patent Publication No. 2011-133851

However, it is generally desired that the photosensitive resin composition for forming a black matrix can form a black matrix exhibiting a high resistance value. In recent years, the demand for this point has become even higher, and even in the photosensitive resin composition described in Patent Document 1, there is a problem that it is difficult to form a black matrix having a high resistance to a desired degree. It was.

It is conceivable that such a problem may occur in the step of heating the resin composition. That is, it is conceivable that by subjecting the acrylic resin to a heating step after forming the black matrix, thermal deformation and thermal deterioration of the acrylic resin occur, and the pigments contained therein come close to each other.
In order to eliminate such a phenomenon, it is conceivable to use a resin having a cardo structure as an alkali-soluble resin in the photosensitive resin composition, or to use a large amount of an alkali-soluble resin having excellent heat resistance such as novolak resin. Be done.
However, when a resin having a cardo structure is excessively contained as an alkali-soluble resin, it tends to be difficult to form a black matrix having excellent water resistance. Further, when a novolak resin is used instead of the acrylic resin, there is a concern that it is difficult to obtain a photosensitive resin composition having good sensitivity.
That is, in the present technical field, there is a fact that a resin composition having an excellent balance of high resistance, high water resistance, and high sensitivity is required, and it is possible to meet such a demand only by selecting an alkali-soluble resin. There was a limit.

The present invention has been made in view of the above problems, and is a photosensitive resin composition capable of forming a black matrix having high resistance and excellent water resistance, and having excellent sensitivity, and the resin composition is cured. It is an object of the present invention to provide a black matrix, a display device including the black matrix, and a method for producing a black matrix using the above-mentioned resin composition.

The present inventors are photosensitive including (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-shielding material, and (E) an epoxy compound. In the resin composition, a resin having an aromatic ring in the main chain is used as the (A) alkali-soluble resin, and an epoxy compound having a specific structure containing an aromatic group and having an average molecular weight of 800 or more is used as the (E) epoxy compound. It has been found that the above-mentioned problems can be solved by using the above-mentioned problem, and the present invention has been completed. Specifically, the present invention provides the following.

（式（Ｅ１）中、ＯＧｌｙは、グリシジルオキシ基であり、Ｒ^ｅ１は、ハロゲン原子又は炭素原子数１〜８の１価の基であり、ａは０〜４の整数であり、ｂは括弧内のユニットの繰り返し数であり、ａが２以上の整数である場合、ベンゼン環上で隣接する２つのＲ^ｅ１は、互いに結合して環を形成してもよく、Ｒ^ｅ２は、２価の脂肪族環式基、又は下記式（Ｅ１−１）：

で表される基であり、式（Ｅ１−１）中、ＯＧｌｙは、グリシジルオキシ基であり、Ｒ^ｅ３は、芳香族炭化水素基であり、Ｒ^ｅ４は、ハロゲン原子、又は炭素原子数１〜４のアルキル基であり、ｃは０又は１であり、ｄは０〜８の整数であり、Ｒ^ｅ５は、水素原子、又は下記式（Ｅ１−２）：

で表される基であり、式（Ｅ１−２）中、ＯＧｌｙは、グリシジルオキシ基であり、Ｒ^ｅ６は、ハロゲン原子、炭素原子数１〜４のアルキル基、又はフェニル基であり、ｅは０〜４の整数である。）
で表されるエポキシ化合物を含有し、
式（Ｅ１）で表されるエポキシ化合物の平均分子量が８００以上である、樹脂組成物である。 A first aspect of the present invention is a resin composition used for forming a black matrix.
(A) Alkali-soluble resin and
(B) Photopolymerizable compound and
(C) Photopolymerization initiator and
(D) Shading material and
(E) Epoxy compound and
Including
(A) The alkali-soluble resin contains a resin containing an aromatic ring in the main chain,
The epoxy compound (E) has the following formula (E1):

(In the formula (E1), OGly is a glycidyloxy group, R ^e1 is a halogen atom or a monovalent group having 1 to 8 carbon atoms, a is an integer of 0 to 4, and b is a parenthesis. When a is an integer of 2 or more, which is the number of repetitions of the unit in the benzene ring, two adjacent ^{Re 1s} on the benzene ring may be bonded to each other to form a ring, and ^{Re 2} is divalent. Aliphatic cyclic group or the following formula (E1-1):

A a group represented by wherein (E1-1), OGly is glycidyloxy ^{group, R e3} is an aromatic hydrocarbon ^{group, R e4} is a halogen atom, or a number of carbon atoms 1 It is an alkyl group of 4, c is 0 or 1, d is an integer of 0 to 8, and ^Re5 is a hydrogen atom or the following formula (E1-2):

In the formula (E1-2), OGly is a glycidyloxy group, R ^e6 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and e is a group represented by. It is an integer from 0 to 4. )
Contains an epoxy compound represented by
A resin composition having an average molecular weight of 800 or more of the epoxy compound represented by the formula (E1).

A second aspect of the present invention is a black matrix obtained by curing the resin composition according to the first aspect.

A third aspect of the present invention is a display device including the black matrix according to the second aspect.

A fourth aspect of the present invention is
A step of forming a coating film by applying the resin composition according to the first aspect, and
The process of regioselectively exposing the coating film and
The process of developing the exposed coating film to form a patterned cured film,
A method for producing a black matrix, which comprises a step of baking a patterned cured film.

According to the present invention, by using the (E) epoxy compound having a specific constitution, it is possible to realize high resistance of the cured film and impartation of high water resistance without excessively impairing the sensitivity of the composition. Can be done.
Therefore, according to the present invention, a photosensitive resin composition capable of forming a black matrix having high resistance and excellent water resistance and having excellent sensitivity, a black matrix obtained by curing the resin composition, and the black matrix are used. It is possible to provide a display device provided and a method for producing a black matrix using the above-mentioned resin composition.

Hereinafter, the present invention will be described based on preferred embodiments. In addition, "~" in this specification represents the above (lower limit value) to the following (upper limit value) unless otherwise specified.

≪Resin composition≫
The resin composition of the present embodiment contains (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-shielding material, and (E) an epoxy compound. ..
In the present embodiment, the alkali-soluble resin (A) contains a resin containing an aromatic ring in the main chain.
Further, the epoxy compound (E) contains an epoxy compound having a specific structure represented by the formula (E1) described later. The average molecular weight of the epoxy compound represented by the formula (E1) is 800 or more.
In the present embodiment, the resin composition contains a resin containing an aromatic ring in the main chain as (A) an alkali-soluble resin, and (E) an epoxy compound having a predetermined structure and a predetermined average molecular weight, which will be described later. By including it, a black matrix having high resistance and excellent water resistance can be formed, and a photosensitive resin composition having excellent sensitivity can be obtained.

Hereinafter, essential or arbitrary components contained in the resin composition and a method for preparing the resin composition will be described.

<(A) Alkali-soluble resin>
The resin composition of the present embodiment contains (A) an alkali-soluble resin (also referred to as "component (A)" in the present specification). The alkali-soluble resin (A) is not particularly limited except that the main chain contains an aromatic ring. From the alkali-soluble resins conventionally blended in various photosensitive resin compositions, a resin containing an aromatic ring in the main chain can be appropriately selected and used as the (A) alkali-soluble resin.
The alkali-soluble resin (A) preferably contains, for example, a resin (a-1) having a cardo structure as an alkali-soluble resin containing an aromatic ring in the main chain. Further, the alkali-soluble resin (A) preferably contains a novolak resin (a-2) or a modified epoxy resin (a-3) described later as an alkali-soluble resin containing an aromatic ring in the main chain. Examples of the alkali-soluble resin containing an aromatic ring in the main chain other than these include aromatic polyamic acid and alkali-soluble aromatic polyester resin.
Further, in the resin composition of the present embodiment, as the alkali-soluble resin (A), at least a resin (a-1) having a cardo structure and a novolak resin (a-2) or a modified epoxy resin (a-3). It is also preferable to use either one in combination.
Here, in the present specification, the (A) alkali-soluble resin refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) having alkali solubility in the molecule.

Examples of the resin suitable as the alkali-soluble resin having an aromatic ring in the main chain include a resin having a cardo structure (a-1) (hereinafter, also referred to as “cardo resin (a-1)”).
When a resin having a (A1) cardo structure is used as the alkali-soluble resin, it is easy to obtain a resin composition having excellent resolution, and it is easy to form a cured film which is difficult to excessively flow by heating using the resin composition.

[Resin having a cardo structure (a-1)]
(A1) As the resin having a cardo skeleton, a resin having a cardo skeleton in its structure and having a predetermined alkali solubility can be used. The cardo skeleton is 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. The second annular structure and the third annular structure may have the same structure or different structures.
A typical example of a cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to a carbon atom at the 9-position of the fluorene ring.

The (A1) cardostructure resin is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (a-1) is preferable.

Wherein ^{(a-1), X} a represents a group represented by the following formula (a-2). m1 represents an integer from 0 to 20.

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 Ra ² independently represents a hydrogen atom or a methyl group, respectively. , ^{R a3} each independently represent an alkylene group of straight or branched chain, m2 represents 0 or 1, ^{W a} represents a group represented by the following formula (a3).

Wherein ^(a-2), as the ^{R a3,} preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms , Ethane-1,2-diyl group, propane-1,2-diyl group, and propane1,3-diyl group are most preferred.

Ring A in formula (a-3) represents an aliphatic ring that may be condensed 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, and adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring that may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

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

^{The divalent group X a} in the formula (a-1) is formed by ^{reacting the tetracarboxylic dianhydride giving the residue Z a} with the diol compound represented by the formula (a-2a) below. A1) Introduced into cardo resin.

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

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.
First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with a group represented by ^{−R a3 −OH according to a conventional method, if necessary.} Glysidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).
Then, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain a diol compound represented by the formula (a-2a).
In the formulas (a-2b) and (a-2c), ^Ra1 , ^Ra3 , and m2 are as described in the formula (a-2). The ring A in the formula (a-2b) and the formula (a-2c) is as described in the formula (a-3).
The method for producing the diol compound represented by the formula (a-2a) is not limited to the above method.

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

In the formula ^{(a-1), R a0} is a group represented by hydrogen or a ^-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 are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic 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 dianhydrides include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. Examples thereof include biphenyl ether tetracarboxylic dianhydride and the like.
Further, in the above formula (a-1), m represents an integer of 0 to 20.

（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１〜１０のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍ３は、０〜１２の整数を示す。）

(In the formula (a-4), R ^a4 , R ^a5 , and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. , M3 indicates an integer from 0 to 12.)

^{The alkyl group that can be selected as Ra4} in the formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms contained in the alkyl group in this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms thereof is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and 1 to 3 from the viewpoint that a cardo resin having excellent heat resistance can be easily obtained. Is 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 preferable independently from the viewpoint that a cardo resin having excellent heat resistance can be easily obtained. ^{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.
^{The plurality of Ra4s} in the formula (a-4) are preferably the same group because it is easy to prepare a high-purity tetracarboxylic dianhydride.

M3 in the formula (a-4) represents an integer from 0 to 12. Purification of the tetracarboxylic dianhydride can be facilitated by setting the value of m3 to 12 or less.
The upper limit of m3 is preferably 5 and more preferably 3 from the viewpoint of easy purification of tetracarboxylic dianhydride.
From the viewpoint of the chemical stability of the tetracarboxylic dianhydride, the lower limit of m3 is preferably 1 and more preferably 2.
The m3 in the formula (a-4) is particularly preferably 2 or 3.

The alkyl groups having 1 to 10 carbon atoms that can be selected as ^{R a5} and R ^a6 in the formula (a-4) are the same as the alkyl groups having 1 to 10 carbon atoms that can be selected as ^{R a4.}
R ^a5 and R ^a6 have hydrogen atoms or 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 5) because the tetracarboxylic acid dianhydride can be easily purified. It is preferably an alkyl group of 1 to 4, particularly preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic acid dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-Tetracarboxylic acid dianhydride (also known as "norbornane-2-spir-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5'', 6,6'' -Tetracarboxylic dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane) -5,5", 6,6 "-tetra Norbornane-2-anhydrogenate, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (also known as "norbornane-" 2-Spiro-2'-Cyclohexanone-6'-Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid dianhydride"), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''- (methylnorbornane) -5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopropanol-α'- Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic 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, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride , Norbornane-2-spiro-α-cyclononanonone-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'-Spyro-2''-norbornane-5,5' ', 6, 6''-Tetracarboxylic acid dianhydride, Norbornane Nan-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 "-norbornane-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 and the like can be mentioned.

The weight average molecular weight of the (A1) cardo resin is preferably 1000 to 40,000, more preferably 1500 to 30000, and even more preferably 2000 to 10000. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

[Novolak resin (a-2)]
The alkali-soluble resin containing an aromatic ring in the main chain preferably contains a novolak resin (a-2) from the viewpoint of suppressing an excessive heat flow of the black matrix due to heating during post-baking.
As the novolak resin (a-2), various novolak resins conventionally blended in the photosensitive resin composition can be used. The novolak resin (a-2) is preferably one obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

(Phenols)
Examples of the phenols used in producing the novolak resin (a-2) include phenols; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol. , 2,5-Xylenol, 2,6-Xylenol, 3,4-Xylenol, 3,5-Xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols; 2 Alkylphenols such as -isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol, and 3,4 , 5-Trialkylphenols such as trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone. (Each alkyl group has 1 to 4 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 by using the resin composition can be adjusted by adjusting the blending ratio of both.
The blending ratio of m-cresol and p-cresol is not particularly limited, but the molar ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in a ratio within such a range, it is easy to obtain a resin composition capable of forming a black matrix having excellent heat resistance.

A novolak resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. When such a novolak resin is used, it is particularly easy to obtain a resin composition capable of forming a black matrix that is difficult to flow excessively by heating during post-baking.
The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the molar ratio of m-cresol / 2,3,5-trimethylphenol is 70/30 or more and 95/5 or less. Is preferable.

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

(Acid catalyst)
Acid catalysts used in the preparation of novolak resin (a-2) include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphoric acid; formic acid, oxalic acid, acetic acid, diethyl sulfate, and Examples thereof include organic acids such as paratoluene oxalic 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 a viewpoint of resistance to flow by heating of a black matrix formed by using the resin composition. Therefore, as the lower limit value, 2000 is preferable, 5000 is more preferable, 10000 is particularly preferable, 15000 is further preferable, 20000 is most preferable, 50000 is preferable as an upper limit value, 45000 is more preferable, 40,000 is further preferable, and 35000 is most preferable. ..

As the novolak resin (a-2), at least two types having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of large and small ones having different weight average molecular weights, it is possible to balance the developability of the resin composition and the heat resistance of the black matrix formed by using the resin composition.

[Modified epoxy resin (a-3)]
The alkali-soluble resin (A) containing an aromatic ring in the main chain is unsaturated with the epoxy compound (a-3a) from the viewpoint of achieving higher flow resistance during baking and high water resistance of the cured film. The reaction product with the group-containing carboxylic acid (a-3b) may contain a polybasic acid anhydride (a-3c) adduct (a-3). Such an adduct is also referred to as "modified epoxy resin (a-3)".
In the specification of the present application and the scope of claims, a compound that falls under the above definition and does not fall under the above-mentioned resin (a-1) having a cardo structure is a modified epoxy resin (a-3). ).

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

<Epoxy compound (a-3a)>
The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound containing no aromatic group. Often, aromatic epoxy compounds having an aromatic group are preferred.
However, when the polybasic acid anhydride (a-3c) does not contain an aromatic group, an aromatic ring is introduced into the main chain, so that the aromatic epoxy compound having an aromatic group is used as the epoxy compound (a-3a). Used.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound, and a polyfunctional epoxy compound is preferable.

Specific examples of the epoxy compound (a-3a) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin. Functional epoxy resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene diamine, tetraglycidyl bisaminomethylcyclohexane and the like. Glycidylamine type epoxy resin; heterocyclic epoxy resin such as triglycidyl isocyanurate; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-Epoxy propoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy propoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] Trifunctional epoxy resins such as -2-propanol; tetrafunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl can be mentioned.

Further, as the epoxy compound (a-3a), an epoxy compound having a biphenyl skeleton is preferable.
The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in 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 resin composition capable of forming a black matrix having an excellent balance between sensitivity and developability and excellent 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１〜１２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１〜４の整数である。）

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

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. , 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 Examples thereof include a group, an n-nonyl group, an isononyl group, an n-decyl group, an isodecyl group, an n-undecyl group, and an 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 to 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 group. Be done.

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

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

（式（ａ−３ａ−３）中、ｋは、式（ａ−３ａ−２）と同様である。） Among the epoxy compounds represented by the formula (a-3a-2), it is particularly easy to obtain a resin composition having an excellent balance between sensitivity and developability, and therefore 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) is reacted with an unsaturated group-containing carboxylic acid (a-3b).
As the unsaturated group-containing carboxylic acid (a-3b), a monocarboxylic acid containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule is preferable. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-flufurylacrylic acid, α-cyanocinnamic acid, and cinnamic acid. Further, the unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more.

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

The ratio of the amounts 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 (a-3b). The ratio of a-3b) to the carboxylic acid equivalent is usually preferably 1: 0.5 to 1: 2, more preferably 1: 0.8 to 1: 1.25, and 1: 0.9 to 1: 1. .1 is particularly preferable.
When the ratio of the amount of the epoxy compound (a-3a) used and the amount of the unsaturated group-containing carboxylic acid (a-3b) used is 1: 0.5 to 1: 2 in the above equivalent ratio, the crosslinking efficiency Is preferable because it tends to improve.

(Polybasic acid anhydride (a-3c))
The polybasic acid anhydride (a-3c) is an carboxylic acid anhydride having two or more carboxyl groups.
The polybasic acid anhydride (a-3c) is not particularly limited, and is, for example, maleic anhydride, succinic anhydride, phthalic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic 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 , The compound represented by the following formula (a-3c-1), and the compound represented by the following formula (a-3c-2) can be mentioned. Further, the polybasic acid anhydride (a-3c) may be used alone or in combination of two or more.

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

(In the formula (a-3c-2), R ^a8 represents an alkylene group which may have a substituent having 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 resin composition having an excellent balance between sensitivity and developability. Further, the polybasic acid anhydride (a-3c) contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2). Is more preferable.

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

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

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1000 or more and 40,000 or less, and more preferably 2000 or more and 30,000 or less. When the weight average molecular weight is 1000 or more, it is easy to form a black matrix having excellent heat resistance and strength. Further, when it is 40,000 or less, it is easy to obtain a resin composition showing sufficient solubility in a developing solution.

[Acrylic resin (a-4)]
The alkali-soluble resin (A) may contain an acrylic resin (a-4) as long as the object of the present invention is not impaired. Since the acrylic resin usually does not contain an aromatic ring in the main chain, the alkali-soluble resin (A) preferably does not contain the acrylic resin (a-4).

As the acrylic resin (a-4), a resin containing a structural unit derived from (meth) acrylic acid and / or a structural unit derived from another monomer such as (meth) acrylic acid ester can be used. The (meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester is represented by the following formula (a-4-1), and is not particularly limited as long as 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. This organic group may contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be linear, branched or cyclic.

The substituent other than a hydrocarbon group in the organic group R ^a10, the effect is not particularly limited as long as they do not impair the present invention, 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, hydroxyimino group, alkyl ether group, alkyl thioether group, aryl ether group, aryl thioether group, amino group (-NH ₂ , -NHR, -NRR': R and R'independently indicate a hydrocarbon group) and the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched or cyclic.

R ^a10 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. 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 a linear or branched chain, the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of suitable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec. -Pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, Examples include an isodecyl group.

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

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

Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, and N. Examples thereof include -methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

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; and anhydrides of these dicarboxylic acids.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like. Can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, and hydroxyethyl vinyl ether. , Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers; vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether. , Vinyl aryl ethers such as vinyl naphthyl ethers and vinyl anthranyl ethers; and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl ballerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl. Examples thereof include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkylstyrene such as methylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Examples thereof include halostyrene such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene and 4-fluoro-3-trifluoromethylstyrene.

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 to 50% by mass, more preferably 10 to 30% by mass, based on the mass of the acrylic resin.

The weight average molecular weight of the acrylic resin (a-4) is preferably 2000 to 50000, and more preferably 5000 to 30000. Within the above range, the film-forming ability of the resin composition and the developability after exposure tend to be easily balanced.

The content of the alkali-soluble resin (A) is preferably 10 to 65% by mass, more preferably 15 to 50% by mass, based on the total mass of the solid content of the resin composition. Within the above range, it is easy to obtain a resin composition having excellent developability.

When the cardo resin (a-1) is used, the content thereof is preferably 5 to 40% by mass, more preferably 8 to 35% by mass, based on the total mass of the solid content of the resin composition. , 10 to 30% by mass, more preferably.
The content of the novolak resin (a-2) is preferably 0.2 to 12% by mass, more preferably 0.5 to 8% by mass, based on the total mass of the solid content of the resin composition. , 1 to 4% by mass, more preferably.
The content of the modified epoxy resin (a-3) is preferably 0.2 to 20% by mass, more preferably 1 to 15% by mass, based on the total mass of the solid content of the resin composition. It is more preferably 2 to 12% by mass.
By using the above resin in an amount within the above range, it is easy to obtain a resin composition having desired properties.

<(B) Photopolymerizable compound>
The resin composition contains (B) a photopolymerizable compound. As the photopolymerizable compound (B), a monomer having an ethylenically unsaturated group is preferable. Such monomers include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and 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-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivative and the like can be mentioned. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylpropantri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetra acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Ellisritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane, 2-hydroxy-3 -(Meta) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin poly Glycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc. and 2-vidroxyethyl (meth) acrylate), methylenebis (meth) acrylamide, Examples thereof include polyfunctional monomers such as (meth) acrylamide methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacrylic formal. These polyfunctional monomers can be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a polyfunctional monomer having three or more functionalities is preferable because it tends to increase the adhesion of the resin composition to the substrate and the strength of the resin composition after curing. A polyfunctional monomer having a functionality or higher is more preferable, and a polyfunctional monomer having a pentafunctionality or higher is further preferable.
Specifically, a polyfunctional monomer having five or more functionalities is preferably used, and dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate is more preferably used.

The content of the photopolymerizable compound in the resin composition is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the total mass of the solid content of the resin composition. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<(C) Photopolymerization Initiator>
The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

(C) Specifically, as the photopolymerization initiator, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, O-acetyl-1- [6- (2- (2-) Methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy) -2-Methylphenyl] Metanon O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl -4'-Methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-Dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (O-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate , 2,4-Diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene. , 2-Isopropylthioxanthene, 2-Ethylanthraquinone, Octamethylanthraquinone, 1,2-Benz anthraquinone, 2,3-Diphenylanthraquinone, Azobisisobutyronitrile, Benzoylperoxide, Cumenehydroperoxide, 2-Mercaptobenzoimi Dazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p' -Bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 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. -Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl- 4-Dimethylaminobenzoate, 9-phenylaclydin, 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 (trichloromethyl) -s-triazine, 2- [2- (fran-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) Lu) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4) -Methoxy) Phenyl-s-Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-) Bromo-4-methoxy) styrylphenyl-s-triazine and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, particularly preferable ones are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime and etanone. , 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 2- (benzoyloxyimino) -1- [4 -(Phenylthio) phenyl] -1-octanone.

（Ｒ^ｃ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０〜４の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｃ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｃ３は、水素原子、又は炭素原子数１〜６のアルキル基である。） As the photopolymerization initiator, it is also preferable to use an oxime compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group.
n1 is an integer from 0 to 4,
n2 is 0 or 1,
R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent.
R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In the formula (c1), R ^c1 is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent. 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 benzoyloxy which may have a substituent. A 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, and 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 group which may have a substituent, an amino group, 1 , Or an amino group substituted with 2 organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further possessed by the substituent.

When R ^c1 is an alkyl group, the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 6 carbon atoms. When R ^c1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkyl group include 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, Examples thereof include an n-decyl group and an isodecyl group. Further, 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 6 carbon atoms. When R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and 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 , Trt-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 methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 6 carbon atoms. Specific examples of the case where R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and 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 Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^c1 is 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, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10 carbon atoms. When R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14 carbon atoms. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, ^Rc1 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 monocycle containing one or more N, S, O, or such monocycles or such monocycles and a benzene ring are condensed. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiazazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Examples thereof include isoindole, indolidin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxalin. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon. Saturated aliphatic acyl group having 2 to 20 atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and phenyl which may have a substituent and which has 7 to 20 carbon atoms. Examples thereof include an alkyl group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 to 20 carbon atoms, and a heterocyclyl group. Be done. Specific examples of these suitable organic groups are the same as for R ^c1 . Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group and an 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, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c1} further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having a number of 2 to 7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. , Dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When ^{the phenyl group, naphthyl group, and 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 to 4 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 R ^c1 , alkyl groups having 1 to 6 carbon atoms and 1 to 1 carbon atoms have carbon atoms because they are chemically stable, have few steric obstacles, and facilitate the synthesis of oxime ester compounds. A group selected from the group consisting of an alkoxy group of 6 and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

Position R ^c1 is bonded to the phenyl group, the phenyl group R ^c1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group In addition, the 4th or 5th position is preferable, and the 5th position is more preferable. Further, n1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. When R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent contained in the phenyl group or the carbazolyl group is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms. Cycloalkyl group of 10 to 10, cycloalkoxy group of 3 to 10 carbon atoms, saturated aliphatic acyl group of 2 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, saturation of 2 to 20 carbon atoms An aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, and a substituent. It may have a phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, and a substituent. A naphthyl group, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a naphthoyloxy group which may have a substituent. , A naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 1, or 2 Examples thereof include an amino group substituted with an organic group of, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and a substituent. A phenoxycarbonyl group may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, and a naphthoyl group which may have a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a substituent. A good heterocyclylcarbonyl group and the like can be mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or the carbazolyl group may have are 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. For phenylalkyl groups which may have groups, naphthylalkyl groups which may have substituents, heterocyclyl groups which may have substituents, and amino groups substituted with one or two organic groups. , R ^c1 is the same.

In R ^c2 , an alkyl group having 1 to 6 carbon atoms is an example of a substituent when the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent. 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; a phenyl group. Naftyl group; benzoyl group; naphthoyl group; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Group; Monoalkylamino group having an alkyl group with 1 to 6 carbon atoms; Dialkylamino group with an alkyl group with 1 to 6 carbon atoms; Morphorin-1-yl group; Piperazin-1-yl group; Halogen; Nitro Group; cyano group can be mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 to 4 are preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c2, the group represented by the following formula (c2) or (c3) is preferable, and the group represented by the following formula (c2) is more preferable, from the viewpoint that a photopolymerization initiator having excellent sensitivity can be easily obtained. , A group represented by the following formula (c2) in which A is S is particularly preferable.

（Ｒ^ｃ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０〜４の整数である。）

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 to 4. is there.)

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

(R ^c5 and R ^c6 are monovalent organic groups, respectively.)

^{When R c4} in the formula (c2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. ^{A preferred example of the case where R c4} is an organic group in the formula (c2) is an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic group having 2 to 7 carbon atoms. Acrylic group; alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic acyloxy group with 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; alkyl group with 1 to 6 carbon atoms, morpholin A benzoyl group substituted with a group selected from the group consisting of a -1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a monoalkylamino group having 1 to 6 carbon atoms; Examples thereof include a dialkylamino group having an alkyl group of 1 to 6; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; a cyano group.

In R ^c4 , it is substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Benzoyl group; nitro group is preferable, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazine-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.

Further, in the formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^c4, to the bond to the phenyl group R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

^{R c5} in the formula (c3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ^c5 are 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 20 carbon atoms, and 2 to 20 carbon atoms. An alkoxycarbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a carbon atom number 7 which may have a substituent. It may have a phenylalkyl group of ~ 20, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent. Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

^{R c6} in the formula (c3) is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Specific examples of a group suitable 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. Heterocyclyl groups may be mentioned. Among these groups, a phenyl group which may have a substituent is more preferable as R ^{c6, and a 2-methylphenyl group is particularly preferable.}

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms and 1 to 1 carbon atoms. An alkoxy group of 6, 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, and an alkyl having 1 to 6 carbon atoms. Examples thereof include a monoalkylamino group having a group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 to 4 are preferable. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 has a plurality of substituents, the plurality of substituents may be the same or different.

^{R c3} in the formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

Among the oxime ester compounds represented by the formula (c1), the following PI-1 to PI-42 are particularly suitable compounds.

An oxime ester compound represented by the following formula (c4) is also preferable as a photopolymerization initiator.

（Ｒ^ｃ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ８及びＲ^ｃ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよく、Ｒ^ｃ１０は１価の有機基であり、Ｒ^ｃ１１は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０〜４の整数であり、ｎ５は０又は１である。）

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c8 and R ^c9 are a chain alkyl group which may have a substituent and a cyclic organic which may have a substituent, respectively. It is a group or a hydrogen atom, and R ^c8 and R ^c9 may be bonded to each other to form a ring, R ^c10 is a monovalent organic group, and R ^c11 has a hydrogen atom and a substituent. It is an alkyl group having 1 to 11 carbon atoms or an aryl group which may have a substituent, n4 is an integer of 0 to 4, and n5 is 0 or 1.)

Here, as the oxime compound for producing the oxime ester compound of the formula (c4), the compound represented by the following formula (c5) is suitable.

（Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、Ｒ^ｃ１０、ｎ４、及びｎ５は、式（ｃ４）と同様である。）

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4, and n5 are the same as in the formula (c4).)

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is attached to a 6-membered aromatic ring on the fluorene ring in the formula (c4), which is different from the 6-membered aromatic ring attached to the group represented by _{− (CO) n5-.} In the formula (c4), the ^{binding position of R c7} with respect to the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has 1 or more R ^{c7 , one of the 1 or more R c7} is a fluorene ring because the compound represented by the formula (c4) can be easily synthesized. It is preferable to bind to the 2-position of the inside. If R ^c7 is more, a plurality of R ^c7 is independently in may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent. 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 benzoyloxy which may have a substituent. A 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, and a substituent. It has 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 group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. When R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkyl group 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, Examples thereof include an n-decyl group and an isodecyl group. Further, when R ^c7 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, and more preferably 1 to 6. When R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkoxy group 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 and 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 , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c7 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 methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10 and more preferably 3 to 6. Specific examples of the case where R ^c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ^c7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^c7 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 to 21, more preferably 2 to 7. Specific examples of the case where R ^c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and 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 Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^c7 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where R ^c7 is 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, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. When R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. Specific examples of the case where R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c7 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, ^Rc7 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperazine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclyl carbonyl group, the heterocyclyl group contained in the heterocyclyl carbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. Saturated aliphatic acyl group of number 2 to 21, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenylalkyl which may have a substituent and may have 7 to 20 carbon atoms. Examples thereof include a group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent and having 11 to 20 carbon atoms, and a heterocyclyl group. .. Specific examples of these suitable organic groups are the same as for R ^c7 . Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group and an 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, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c7} further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having a number of 2 to 7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. , Dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When ^{the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c7} 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 to 4 is preferable. When ^{the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c7} have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, as R ^c7 , a nitro group or ^{a group represented by R c12-} CO- tends to improve the sensitivity and is preferable. R ^c12 is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as R ^c12 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. A good heterocyclyl group is mentioned. Among these groups, 2-methylphenyl group, thiophen-2-yl group, and α-naphthyl group are particularly preferable as R ^c12.
Further, when R ^c7 is a hydrogen atom, the transparency tends to be good, which is preferable. If R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.

In the formula (c4), R ^c8 and R ^c9 are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ^c8 and R ^c9 may be coupled to each other to form a ring. Among these groups, as R ^c8 and R ^c9 , a chain alkyl group which may have a substituent is preferable. When R ^c8 and R ^c9 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of cases where R ^c8 and R ^c9 are chain alkyl groups 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 Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ^c8 and R ^c9 are alkyl groups, 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. 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 that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when ^{R c7 is a cycloalkyl group.} Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when ^{R c7 is a heterocyclyl group.} When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched chain, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

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

When R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c8 and R ^c9 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^c8 and R ^c9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? , It is preferable that the group is formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. 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, Examples thereof include a tetracyclododecyl group and an adamantyl group.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or such monocycles, or such monocyclic and benzene rings. Is a heterocyclyl group condensed with. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperazine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done.

R ^c8 and R ^c9 may be coupled to each other to form a ring. The group consisting of the ring formed by ^{R c8} and R ^{c9 is preferably a cycloalkylidene group.} When R ^c8 and R ^c9 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When ^{the group formed by combining R c8} and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

Among the R ^c8 and R ^c9 described above, examples of suitable groups 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, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

The ^{number of carbon atoms of the linear alkylene group of A 1} is preferably 1 to 10, and more preferably 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched chain, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. 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 an alkyl halide group, the halogen atom contained in the alkyl halide 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 alkyl halide 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 those of the cyclic organic group that ^{R c8} and R ^{c9 have as substituents.} When A ² is an alkoxycarbonyl group, examples of alkoxycarbonyl groups are similar to the alkoxycarbonyl groups that ^{R c8} and R ^{c9 have as substituents.}

Suitable specific examples of R ^c8 and R ^c9 are 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 Cyanalkyl groups such as −pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl Group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and phenyl such as 8-phenyl-n-octyl group. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy Carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy Carbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-etoki An alkoxycarbonylalkyl group such as a sicarbonyl-n-heptyl group and an 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5- Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4- Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-tri Examples thereof include a fluoropropyl group and an alkyl halide group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among the above-mentioned suitable groups as R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group and 2-phenylethyl group. 2-Cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^c10 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups and substituents ^{, as in R c7.} 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 good 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 group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like. Specific examples of these groups are similar to those described for ^{R c7.} Further, as R ^c10 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained ^{in R c7 may have.}

Among the organic groups, R ^c10 includes an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthio which may have a substituent on the aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that 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 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

^As the ^{R c10,} a group represented by -A 3 ^{-CO-O-A 4} are also preferred. 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, preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

Preferred examples of A ⁴ is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. 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 Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a 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-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group and the like.

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０〜４の整数であり、Ｒ^ｃ１３及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１〜８の整数であり、ｎ８は１〜５の整数であり、ｎ９は０〜（ｎ８＋３）の整数であり、Ｒ^ｃ１５は有機基である。） ^{Although R c10} has been described above, the group represented by the following formula (c4a) or (c4b) is preferable as ^{R c10.}

(In formulas (c4a) and (c4b), R ^c13 and R ^c14 are organic groups, respectively, n6 is an integer of 0 to 4, and R ^c13 and R ⁸ are present at adjacent positions on the benzene ring. , R ^c13 and R ^c14 may be combined with each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, and n9 is an integer of 0 to (n8 + 3). ^Yes , R c15 is an organic group.)

Examples of organic groups for ^{R c13} and R ^{c14 in} formula (c4a) are similar to ^{R c7.} As R ^c13 , an alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms thereof is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 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 (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalene-1-yl group and 1,2,3,4-. Examples thereof include a tetrahydronaphthalene-5-yl group. In the above formula (c4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the above formula (c4b), R ^c15 is an organic group. ^Examples of the organic group include groups similar to the organic group described for R c7. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the above formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (c4b), n9 is 0 to (n8 + 3), an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is particularly preferable. In the above formula (c4b), n7 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 the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. A phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed when ^{R c11 is an alkyl group.} Further, ^{as the substituent which may be possessed when R c7} 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 the formula (c4), as R ^c11 , a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified. Of these, a methyl group or a phenyl group is more preferable.

The compound represented by the formula (c4) has an oxime group (> C = N-OH) contained in the compound represented by the above formula (c5) represented by> C = NO-COR ^c11. Manufactured by a method comprising the step of converting to an oxime ester group. R ^c11 are the same as ^{R c11} in formula (c4).

The conversion of the oxime group (> C = N-OH) ^{to the oxime ester group represented by> C = NO-COR c11} is carried out by using the compound represented by the above formula (c5) and an acylating agent. It is done by reacting.
The acylating agent to give the acyl group represented by -COR ^{c11, (R c11} _CO) or an acid anhydride represented by ₂ ^O, R c11 COHal (Hal is a halogen atom) include acid halide represented by Be done.

Preferable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-83.

The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the solid content of the resin composition. By setting the content of the photopolymerization initiator (C) in the above range, it is possible to obtain a resin composition in which defects in the pattern shape are unlikely to occur.

Moreover, you may combine (C) a photopolymerization initiator with a photoinitiator aid. Photoinitiator aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate 2-. Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropion Examples thereof include thiol compounds such as acid, methyl 3-mercaptopropionate, pentaeristol tetramercaptoacetate and 3-mercaptopropionate. These photoinitiator aids can be used alone or in combination of two or more.

<(D) Shading material>
Since the resin composition is used for forming a black matrix, it contains (D) a light-shielding material. The light-shielding material (D) typically preferably contains a black pigment. By using the resin composition containing the black pigment, the cured film formed is imparted with light-shielding properties. Therefore, the resin composition containing a black pigment is suitably used for forming a black matrix in an image display panel such as a liquid crystal display panel.

Examples of black pigments include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides and metal sulfides. Various pigments can be mentioned regardless of organic substances or inorganic substances such as substances, metal sulfates or metal carbonates. Among these black pigments, carbon black is preferable because it is easily available and it is easy to form a cured film having excellent light-shielding properties and high electrical resistance.
The hue of the black pigment is not limited to black, which is an achromatic color in terms of color theory, and may be purplish black, bluish black, or reddish black.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. Moreover, you may use resin-coated carbon black.

As the carbon black, carbon black that has been subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity as defined by Bronsted. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group and the like. The acidic group introduced into the carbon black may form a salt. The cation forming 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 that have been subjected to the treatment for introducing the acidic groups described above, the carboxylic acid group, the carboxylic acid base, from the viewpoint of achieving high resistance of the light-shielding cured film formed by using the resin composition, Carbon black having one or more functional groups selected from the group consisting of a sulfonic acid group and a sulfonic acid base is preferable.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
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, etc., or an indirect substitution method using sulfite, hydrogen sulfite, etc.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method in which an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group are reacted by Williamson's 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 of deprotecting carbon black after carrying out a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

Among these methods, method 2) is preferable because the process of introducing an acidic group is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of acidic groups 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 the carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol with respect to 100 g of the carbon black.

The carbon black into which the acidic group has been introduced may be coated with a resin.
When a resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. The coating treatment with the resin does not cause any adverse effect on the dielectric constant of the light-shielding cured film formed by using the resin composition. Examples of resins that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, and polystyrene, polycarbonate, polyethylene terephthalate, and poly. Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylensulphon, polyarylate, and polyether ether ketone. The amount of the resin coated on the carbon black is preferably 1 to 30% by mass with respect to the total of the mass of the carbon black and the mass of the resin.

Further, as the black pigment, a perylene-based pigment can also be preferably used. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d-1), a perylene-based pigment represented by the following formula (d-2), and a perylene-based pigment represented by the following formula (d-3). Perylene-based pigments can be mentioned. As commercial products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene-based pigments.

式（ｄ−１）中、Ｒ^ｄ１及びＲ^ｄ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｄ３及びＲ^ｄ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In formula (d-1), R ^d1 and R ^d2 independently represent an alkylene group having 1 to 3 carbon atoms, and R ^d3 and R ^d4 independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a hydrogen atom, respectively. Represents an acetyl group.

式（ｄ−２）中、Ｒ^ｄ５及びＲ^ｄ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

In formula (d-2), R ^d5 and R ^d6 independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｄ−３）中、Ｒ^ｄ７及びＲ^ｄ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｄ７及びＲ^ｄ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (d-3), R ^d7 and R ^d8 are independent alkyl groups having a hydrogen atom and 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P, respectively. Good. When R ^d7 and R ^d8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) are, for example, JP-A-62-1753. , No. 63-26784 can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

In order to disperse the perylene-based pigment well in the resin composition, the average particle size of the perylene-based pigment is preferably 10 to 1000 nm.

Further, the light-shielding material (D) may contain a lactam pigment. Examples of the lactam pigment include compounds represented by the following formula (d-4).

In formula (d-4), X ^d represents a double bond and is independently E-form or Z-form as geometric isomers, and R ^d9 is independently hydrogen atom, methyl group, nitro group, and methoxy. A group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, R ^d10 independently indicates a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 independently indicates a hydrogen atom. , Methyl group, or chlorine atom.
The compound represented by the formula (d-4) can be used alone or in combination of two or more.
R ^d9 is preferably bonded to the 6-position of the dihydroindron ring because the compound represented by the formula (d-4) can be easily produced, and R ^d11 is bonded to the 4-position of the dihydroindron ring. It is preferable to do so. From the same viewpoint, R ^d9 , R ^d10 , and R ^d11 are preferably hydrogen atoms.
The compound represented by the formula (d-4) has an EE form, a ZZ form, and an EZ form as geometric isomers, but may be a single compound of any one of these, or these geometric isomers. May be a mixture of.
The compound represented by the formula (d-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the lactam pigment well in the resin composition, the average particle size of the lactam pigment is preferably 10 to 1000 nm.

Further, fine particles containing silver-tin (AgSn) alloy as a main component (hereinafter, referred to as "AgSn alloy fine particles") are also preferably used as the black pigment. The AgSn alloy fine particles may be mainly composed of the AgSn alloy, and may contain, for example, Ni, Pd, Au, etc. as other metal components.
The average particle size of the AgSn alloy fine particles is preferably 1 to 300 nm.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x in which a chemically stable AgSn alloy can be obtained is 1 ≦ x ≦ 10, and the range of x in which both chemical stability and blackness can be obtained at the same time is. 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is obtained in the range of x above,
When x = 1, Ag / AgSn = 0.4762
When x = 3, 3.Ag / Ag3Sn = 0.7317
When x = 4, 4. Ag / Ag4Sn = 0.7843
When x = 10, 10 · Ag / Ag10Sn = 0.9008
Will be.
Therefore, this AgSn alloy becomes chemically stable when it contains 47.6 to 90% by mass of Ag, and is effective with respect to the amount of Ag when it contains 73.17 to 78.43% by weight of Ag. Chemical stability and blackness can be obtained.

The AgSn alloy fine particles can be produced by using a usual fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray pyrolysis method, an atomizing method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

The AgSn alloy fine particles have high insulating properties, but the surface may be covered with an insulating film in order to further enhance the insulating properties of the black matrix. As a material for such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, insulating metal oxides such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (itria), titanium oxide (titania) and the like are preferably used. Be done.
Further, as the organic polymer compound, a resin having an insulating property, for example, a polyimide, a polyether, a polyacrylate, a polyamine compound or the like is preferably used.

The thickness of the insulating film is preferably 1 to 100 nm, more preferably 5 to 50 nm in order to sufficiently enhance the insulating property of the surface of the AgSn alloy fine particles.
The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, it is preferable to use an alkoxide such as tetraethoxysilane or aluminum triethoxyde because an insulating film having a uniform film thickness can be formed at a relatively low temperature.

As the black pigment, the above-mentioned perylene-based pigment, lactam-based pigment, and AgSn alloy fine particles may be used alone, or these may be used in combination.
In addition, the black pigment may contain a pigment having a hue such as red, blue, green, or yellow for the purpose of adjusting the color tone. The dye having another hue of the black pigment can be appropriately selected from known dyes. For example, as the pigment having another hue of the black pigment, the above-mentioned various pigments can be used. The amount of the black pigment having a hue other than that of the black pigment is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the black pigment.

In order to uniformly disperse the light-shielding material (D) described above in the resin composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the (D) light-shielding material, it is preferable to use an acrylic resin-based dispersant or a urethane resin-based dispersant as the dispersant.
In addition, corrosive gas caused by the dispersant may be generated from the cured film. Therefore, it is also an example of a preferable embodiment that the light-shielding material (D) is dispersed without using a dispersant.

Further, as the (D) light-shielding material, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when they are used in combination, they are organic with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. The pigment is preferably used in the range of 10 to 80 parts by mass, and more preferably used in the range of 20 to 40 parts by mass.

In the resin composition, a pigment may be used in combination with a dye as the (D) light-shielding material. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the resin composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes and the like. Can be done.
Further, these dyes can be raked (chlorinated) to be dispersed in an organic solvent or the like, and this can be used as (D) a light-shielding material.
In addition to these dyes, for example, JP2013-225132A, JP2014-178477A, JP2013-137543A, JP2011-38085, JP2014-197206, etc. The dyes and the like described can also be preferably used.

The amount of the light-shielding material (D) used in the resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically 2 to 75% by mass with respect to the total mass of the solid content of the resin composition. Is preferable, and 3 to 70% by mass is more preferable.

The light-shielding material (D) is preferably a dispersion liquid dispersed in the presence or absence of a dispersant at an appropriate concentration, and then added to the resin composition.
In this specification, the amount of the above-mentioned (D) light-shielding material used can be defined as a value including the existing dispersant.

<(E) Epoxy compound>
The resin composition contains an epoxy compound (E) represented by the formula (E1) described later.

（式（Ｅ１）中、ＯＧｌｙは、グリシジルオキシ基であり、Ｒ^ｅ１は、ハロゲン原子、又は炭素原子数１〜８の１価の基であり、ａは０〜４の整数であり、ｂは括弧内のユニットの繰り返し数であり、ａが２以上の整数である場合、ベンゼン環上で隣接する２つのＲ^ｅ１は、互いに結合して環を形成してもよく、Ｒ^ｅ２は、２価の脂肪族環式基、又は下記式（Ｅ１−１）：

で表される基であり、式（Ｅ１−１）中、ＯＧｌｙは、グリシジルオキシ基であり、Ｒ^ｅ３は、芳香族炭化水素基であり、Ｒ^ｅ４は、ハロゲン原子、又は炭素原子数１〜４のアルキル基であり、ｃは０又は１であり、ｄは０〜８の整数であり、Ｒ^ｅ５は、水素原子、又は下記式（Ｅ１−２）：

で表される基であり、式（Ｅ１−２）中、ＯＧｌｙは、グリシジルオキシ基であり、Ｒ^ｅ６は、ハロゲン原子、炭素原子数１〜４のアルキル基、又はフェニル基であり、ｅは０〜４の整数である。） The epoxy compound represented by the formula (E1) will be described below.

(In the formula (E1), OGly is a glycidyloxy group, R ^e1 is a halogen atom or a monovalent group having 1 to 8 carbon atoms, a is an integer of 0 to 4, and b is an integer of 0 to 4. When the number of repetitions of the unit in parentheses and a is an integer of 2 or more, two adjacent ^{Re 1s} on the benzene ring may be bonded to each other to form a ring, and ^{Re 2} is divalent. Aliphatic cyclic group, or the following formula (E1-1):

A a group represented by wherein (E1-1), OGly is glycidyloxy ^{group, R e3} is an aromatic hydrocarbon ^{group, R e4} is a halogen atom, or a number of carbon atoms 1 It is an alkyl group of 4, c is 0 or 1, d is an integer of 0 to 8, and ^Re5 is a hydrogen atom or the following formula (E1-2):

In the formula (E1-2), OGly is a glycidyloxy group, R ^e6 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and e is a group represented by. It is an integer from 0 to 4. )

The epoxy compound represented by the above formula (E1) has an average molecular weight of 800 or more. By using a compound having such an average molecular weight as the epoxy compound represented by the formula (E1), it is easy to obtain a resin composition capable of forming a black matrix having high resistance and excellent water resistance and strength.
The average molecular weight of the epoxy compound represented by the formula (E1) is preferably 1000 or more, more preferably 1200 or more, and particularly preferably 1500 or more. The average molecular weight of the epoxy compound represented by the formula (E1) is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint of making it difficult to generate a residue during development.

In the formula (E1), ^Re1 is a halogen atom or a monovalent group having 1 to 8 carbon atoms. Specific examples of monovalent groups having 1 to 8 carbon atoms include an alkyl group, an alkoxy group, a phenoxy group, an aliphatic acyl group, an aliphatic acyloxy group, a benzoyl group, a benzyl group, a phenethyl group, and an unsaturated aliphatic group. Examples include hydrocarbon groups.
The alkyl group, alkoxy group, aliphatic acyl group, aliphatic acyloxy group, and unsaturated aliphatic hydrocarbon group may be linear or branched.

^{Preferable examples of the halogen atom as Re 1} include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferable examples of the alkyl group as R ^e1 are 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, preferably a methyl group. , And an ethyl group are more preferred.

When ^Re1 is a monovalent group having 1 to 8 carbon atoms, the monovalent group is preferably an alkyl group or an alkoxy group.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. Examples include n-heptyl group, n-octyl group, and 2-ethylhexyl group.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group and n. Included are −hexyloxy group, n-heptyloxy group, n-octyloxy group, and 2-ethylhexyloxy group.

Further, when a is an integer of 2 to 4, 2 ^{Re 1s} adjacent to each other on the benzene ring among the ^{plurality of Re 1s} may be bonded to each other to form a ring. The ^{ring formed by combining R e1 of} 2 may be an aromatic ring or an aliphatic ring, and may be a hydrocarbon ring or a heterocycle.
When the ^{ring formed by combining R e1 of} 2 is a heterocycle, examples of the heteroatom contained in the ring include N, O, S, and Se.
Preferable examples of the group formed together with the benzene ring by the bond of R ^{e1 of 2 include a naphthalene ring and a tetralin ring.}

In the formula (E1), the ^{divalent aliphatic cyclic group as Re} 2 is not particularly limited, and may be a heterocyclic group having two or more rings of a monocyclic group. The divalent aliphatic cyclic group usually does not contain an epoxy group in its structure, and preferably does not contain an epoxy group.
Specific examples of the divalent aliphatic cyclic group include groups obtained by removing two hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples thereof include monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane from which two hydrogen atoms have been removed.
The number of carbon atoms of the divalent aliphatic cyclic group is preferably 3 to 50, more preferably 3 to 30, and particularly preferably 3 to 20. Most preferably 3 to 15.

Specific examples of the divalent aliphatic cyclic group for R ^e2 include the groups shown below.

^Re3 is an aromatic hydrocarbon group. The valence of the aromatic hydrocarbon group as R ^e3 is a 2 + c + d. The aromatic hydrocarbon group is not particularly limited. The aromatic hydrocarbon ring constituting the aromatic hydrocarbon group is typically a 6-membered aromatic hydrocarbon ring (benzene ring) or two or more benzene rings fused to each other or bonded via a single bond. It is a ring.
Preferable specific examples of the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group are benzene, naphthalene, anthracene, phenanthrene, biphenyl, and terphenyl. These aromatic hydrocarbon rings 2 + c + d pieces of groups excluding the hydrogen atom are preferred as the aromatic hydrocarbon group as R ^e3.

In the group represented by the formula (E1-1), c is 0 or 1. That is, a glycidyloxy group may not be bonded to ^Re3 , which is an aromatic hydrocarbon group, and one glycidyloxy group may be bonded.

In the group represented by the formula ^{(E1-1), R e4} is a halogen atom, or an alkyl group having 1 to 4 carbon atoms, d is an integer of 0-8. ^{That, R e4} are on ^{R e3} is an aromatic hydrocarbon group, a substituent other than glycidyl ^group, a substituted radix 0-8 on ^{R e3.} d is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
^{Preferable examples of the halogen atom as Re4} include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ^{Preferable examples of the alkyl group as Re4} are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group, preferably a methyl group. , And an ethyl group are more preferred.

In the group represented by the formula ^{(E1-1), R e5} is a hydrogen atom, or a group represented by the aforementioned formula (E1-2).
Re6 in the formula (E1-2) is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Specific examples of the halogen atom and the alkyl group having 1 to 4 carbon atoms are the same as those of ^Re4.

The epoxy compound represented by the formula (E1) described above, R ^e2 is either a divalent aliphatic cyclic group, or a divalent group represented by the aforementioned formula (E1-1) It is preferable that c is 0 and ^Re5 is a group which is a hydrogen atom.
In this case, better water resistance of the black matrix is achieved by the presence of an appropriate distance between the plurality of epoxy groups contained in the epoxy compound represented by the formula (E1).

The epoxy compound represented by the formula (E1) is available as a commercial product. Specific examples of commercially available products include NC-series and XD-series manufactured by Nippon Kayaku Co., Ltd. In addition, equivalent products having a specific structure can be obtained from DIC Corporation and Showa Denko Corporation.

The chemical structures of suitable specific examples of the epoxy compound represented by the formula (E1) are described below. In the following formula, OGly represents a glycidyloxy group, and p represents the number of repetitions of the unit in parentheses.

The epoxy compound (E) described above may contain other epoxy compounds together with the epoxy compound represented by the formula (E1) as long as the object of the present invention is not impaired.
The other epoxy compounds are not particularly limited, but preferred compounds include the epoxy compounds mentioned as specific examples of the above-mentioned epoxy compound (a-3a).
The ratio of the mass of the epoxy compound represented by the formula (E1) to the mass of the epoxy compound (E) is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. Most preferably.

As for the amount of the (E) epoxy compound used described above, the total amount (number of moles) of the active hydrogen groups of the above-mentioned (A) alkali-soluble resin is Am, and the total amount of the epoxy groups of the (E) epoxy compound. When (number of moles) is Em, Am / Em is preferably in the range of 0.25 or more and 4.0 or less, and more preferably in the range of 0.5 or more and 2.0 or less.
By using the amount of the (E) epoxy compound in such a range, it is easy to form a black matrix having excellent water resistance and strength.

The content of the epoxy compound (E) in the total solid content of the resin composition is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.
Further, the content of the epoxy compound represented by the above formula (E1) in the total solid content of the resin composition is preferably 0.5% by mass or more and 10% by mass or less, and 1% by mass or more and 5% by mass or less. The following is more preferable.

<(S) Organic solvent>
The resin composition preferably contains (S) an organic solvent in order to improve coatability and adjust the viscosity.

Specifically, as the organic solvent (S), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (Poly) alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc. (Poly) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2- Lactate alkyl esters such as methyl hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate , Ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butylate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and the like. Esters; Aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutylamide, N, N-diethylacetamide , N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and nitrogen-containing polar organic solvents such as N, N, N', N'-tetramethylurea; etc. Can be mentioned.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, lactic acid alkyl esters, and other esters described above are preferable, and alkylene glycol monoalkyl ether acetates described above. Other ethers, other esters described above such as benzyl acetate are more preferred.
Further, it is also preferable that the (S) organic solvent contains a nitrogen-containing polar organic solvent in terms of the solubility of each component and the dispersibility of the (D) light-shielding material. As the nitrogen-containing polar organic solvent, N, N, N', N'-tetramethylurea and the like can be used.
These solvents can be used alone or in combination of two or more.

The content of the organic solvent (S) is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. The viscosity of the resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and even more preferably 20 to 30 cp. The solid content concentration is preferably 5 to 100% by mass, more preferably 15 to 50% by mass.

<Other ingredients>
The resin composition contains, if necessary, an epoxy compound other than the (E) epoxy compound, a surfactant, an adhesion improver, a thermal polymerization inhibitor, a defoaming agent, an additive such as a silane coupling agent, and the like. be able to. As any of the additives, conventionally known ones can be used.
The resin composition preferably contains a silane coupling agent because it has a good shape and easily forms a black matrix having excellent adhesion to a substrate. As the silane coupling agent, conventionally known ones can be used without particular limitation.
Examples of the surfactant include anionic, cationic, nonionic and the like compounds, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the defoaming agent include silicone and fluorine. Examples include compounds.

By using the resin composition described above, a cured film having a low volume resistivity and a high optical density (OD value) can be formed.
Specifically, the resin composition can provide a cured film having a volume resistivity of preferably 1.0 × 10 ¹⁰ Ω · cm or more, more preferably 1.0 × 10 ^{11 Ω · cm or more.} Further, the resin composition of the present embodiment has an optical density (OD value) of preferably 2.5 / μm or more, more preferably 3.0 / μm or more, still more preferably 3.5 / μm or more, and is cured. A membrane can be given.
In the black matrix, these physical property values are generally likely to be trade-offs, but in the present embodiment, both of these physical characteristics can be satisfied.

<Preparation method of resin composition>
The resin composition described above can be obtained by mixing each of the above components in a predetermined amount and then uniformly mixing them with a stirrer. In addition, you may filter using a filter so that the obtained mixture becomes more uniform.

≪Manufacturing method of black matrix≫
As a method for producing a black matrix, a conventionally known method using (B) a photosensitive resin composition for forming a black matrix containing a photopolymerizable compound can be adopted without particular limitation.

A suitable method for producing a black matrix is
The process of forming a coating film by applying the above-mentioned resin composition and
The process of regioselectively exposing the coating film and
The process of developing the exposed coating film to form a patterned cured film,
Examples thereof include a step of baking a patterned cured film and a method including.

In order to form a black matrix using a resin composition, first, the resin composition is applied onto a substrate selected according to the method and configuration of an image display device to form a coating film. The method for forming the coating film is not particularly limited, but for example, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used. Be told.

The applied resin composition is dried, if necessary, to form a coating film. The drying method is not particularly limited, for example, (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, and (2) several hours at room temperature. Examples include a method of leaving the solvent for several days, and (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, the coating film is exposed. The exposure is performed by irradiating with active energy rays such as ultraviolet rays and excimer laser light. The exposure is regioselective so that a black matrix of a desired pattern is formed, for example, by a method of performing exposure through a negative mask. The energy dose to be irradiated varies depending on the composition of the resin composition, but is preferably about ^{40 to 200 mJ / cm 2 for example.}
When the entire surface of the coating film is exposed, an unpatterned cured film having a shape corresponding to the shape of the coating film is formed.

When the coating film is exposed position-selectively, the unexposed portion is dissolved in the developing solution and removed by developing the exposed film with a developing solution to form a patterned cured film. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer is appropriately selected according to the composition of the resin composition. As the developer, for example, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt can be used.

Next, baking (post-baking) is performed on the patterned cured film. The bake temperature is not particularly limited, but is preferably 180 to 250 ° C, more preferably 220 to 230 ° C. The bake time is typically 10 to 90 minutes, preferably 20 to 60 minutes.
By baking as described above, a cured film of a resin composition that can be suitably used as a black matrix can be obtained.

The black matrix formed in this way can be suitably used in various image display devices represented by liquid crystal display devices.

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

[Preparation Example 1]
First, in a 500 ml four-necked flask, 235 g of bisphenol fluoride 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. Was charged, and the mixture was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was cloudy, and the solution was heated to 120 ° C. to completely dissolve it. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate thus obtained to dissolve it, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, gradually heated, 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 was mixed and reacted at 90 ° C. for 6 hours to obtain resin A-1. The disappearance of the acid anhydride group was confirmed by the IR spectrum.

[Example 1, Comparative Examples 1 to 4]
In Examples and Comparative Examples, a cardo resin and a novolak resin were used as the (A) alkali-soluble resin.
As the cardo resin, the resin A-1 obtained in Preparation Example 1 above was used.
As the novolak resin, TO-547 (trade name) manufactured by Sumitomo Bakelite Co., Ltd. was used. TO-547 is a cresol of Mw30000 obtained by adding oxalic acid and a concentration of 37% by mass formalin to a mixture of 90 mol% m-cresol and 10 mol% 2,3,5-trimethylphenol and conducting a condensation reaction by a conventional method. It is a novolak resin.
In Comparative Example 2, a styrene-methacrylic acid copolymer was used as the (A) alkali-soluble resin.
In Comparative Example 3, the vinyl group-containing acrylic resin obtained by the following preparation method was used as the (A) alkali-soluble resin.

[Preparation method of vinyl group-containing acrylic resin]
Methacrylic acid and benzyl methacrylate are copolymerized at a ratio of 45 mol%: 55 mol% to obtain a copolymer, and this copolymer is further reacted with 3,4-epoxycyclohexylmethylmethacrylate to obtain vinyl. A group-containing acrylic resin was obtained. The amount of 3,4-epoxycyclohexylmethylmethacrylate used here was 15 mol% when the amount of methacrylic acid was 45 mol%.

In Examples and Comparative Examples, DPHA (dipentaerythritol hexaacrylate) was used as the (B) photopolymerizable compound.

In Examples and Comparative Examples, as the (C) photopolymerization initiator, OXE-02 (trade name, manufactured by BASF, Inc., O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole) −3-Il] Etanone oxime) was used.

In Examples and Comparative Examples, carbon black was used as the (D) light-shielding material.
As the carbon black, carbon black (pigment A (dispersion liquid)) manufactured by Mikuni Color Co., Ltd. was used.
In Table 1 of this Example section, the total value of the solid content of the pigment and the dispersant is described.

In Example 1, as the (E) epoxy compound, an epoxy compound E1 (NC-2000-L, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 229 to 244) having the following structure was used. In addition, p in the following formula represents the number of repetitions of the unit in parentheses, but in this example, an epoxy compound having an average molecular weight of 1700 was used.

The amounts of (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) light-shielding material, and (E) epoxy compound shown in Table 1 are used, respectively. , (S) Dissolved and dispersed in an organic solvent so as to have a solid content concentration of 15% by mass to obtain the resin composition of Example 1.
Further, the amounts of (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photopolymerization initiator, and (D) light-shielding material shown in Table 1 are respectively (S) organic. The resin compositions of Comparative Examples 1 to 4 were obtained by dissolving and dispersing in a solvent so as to have a solid content concentration of 15% by mass.
As the organic solvent (S), a mixed solvent of 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: cyclohexanone = 40: 35: 25 (mass ratio) was used.
Using the obtained resin composition, resistance evaluation, sensitivity evaluation, solubility evaluation, water resistance evaluation, and film strength evaluation were evaluated according to the following methods.

<Resistance evaluation>
First, a 100 mm square glass substrate was washed with pure water and dried in an oven at 160 ° C. The resin compositions obtained in Examples and Comparative Examples were applied to a dried glass substrate and heated on a hot plate at 100 ° C. for 2 minutes to volatilize the solvent. Immediately after that, exposure was performed at an exposure amount of 30 mJ / cm ² using Mask without a light-shielding pattern, and a developer solution was applied for 70 seconds using a KOH aqueous solution having a concentration of 0.04 mass% as a developer solution.
The prepared substrate was held in an oven heated to 230 ° C. for 180 minutes and then cooled to obtain a black film. The black film obtained in Examples and Comparative Examples had an optical density (OD value) of more than 4.0 / μm.
The volume resistivity of the obtained black film was measured, and the resistance of the black matrix formed using the resin composition was evaluated according to the following criteria.
This item was evaluated based on the following criteria.
◯: The volume resistivity is 1.0 × 10 ¹⁰ Ω · cm or more.
X: Volume resistivity is ^{less than 1.0 × 10 10} Ω · cm.

<Sensitivity evaluation>
First, a 100 mm square glass substrate was washed with pure water and dried in an oven at 160 ° C. The resin compositions obtained in Examples and Comparative Examples were applied to a dried glass substrate with a spin coater to obtain a coating film having a film thickness of 1.3 μm. Immediately thereafter, it was exposed with a 5 μm line Mask in ^{an exposure range of 30 to 50 mJ / cm 2} , and developed for 70 seconds using a KOH solution having a concentration of 0.04 mass% as a developer. The exposure was carried out by a Proximity exposure machine manufactured by Topcon Co., Ltd. under the conditions of Gap 70 μm and illuminance 20 mw.
This item was evaluated based on the following criteria.
⊚: An exposure amount of ^{30 mJ / cm 2} or more and less than 35 mJ / cm ² was required to obtain a pattern of 5 μm.
◯: An exposure amount of ^{35 mJ / cm 2} or more and less than 40 mJ / cm ² was required to obtain a pattern of 5 μm.
X: An exposure amount of ^{40 mJ / cm 2} or more was required to obtain a pattern of 5 μm.

<Solubility evaluation>
First, a 100 mm square glass substrate was washed with pure water and dried in an oven at 160 ° C. The resin compositions obtained in Examples and Comparative Examples were applied to a dried glass substrate with a spin coater to obtain a coating film having a film thickness of 1.3 μm. Immediately after that, it was exposed with a mask of 5 μm line at an exposure amount of 30 mJ / cm ² , and developed for 70 seconds using a KOH solution having a concentration of 0.04 mass% as a developer. The exposure was carried out by a Proximity exposure machine manufactured by Topcon Co., Ltd. under the conditions of Gap 70 μm and illuminance 20 mw.
This item was evaluated based on the following criteria.
◯: BreakPoint (time for a part of the unexposed portion to dissolve) is 35 seconds or more and less than 45 seconds.
X: BreakPoint is less than 35 seconds or 45 seconds or more.

<Water resistance evaluation>
The resin composition was applied, exposed, and brought into contact with the developing solution on the glass substrate by the same method as the resistance evaluation. Then, the substrate was held in an oven heated to 230 ° C. for 60 minutes. By allowing this to cool, a substrate having a black film was obtained. The formed black film was immersed in pure water and stored for 12 hours in an atmosphere of 2 atm, 120 ° C. and 100% humidity to evaluate water resistance.
In this item, the adhesiveness of the black film was evaluated based on the cross-cut method specified in JIS5600-5-6 (1999). The specific evaluation criteria are as follows.
⊚: With respect to the black film on the substrate, the area of the peeled portion is 10% or less.
◯: Regarding the black film on the substrate, the area of the peeled portion is more than 10% and 30% or less.
X: The area of the black film on the substrate to be peeled off is more than 30%.

<Membrane strength evaluation>
A black film was formed in the same manner as in the water resistance evaluation. The substrate was cut into 20 mm squares, and a ceramic anti-deflection plate was attached to the back surface. An aluminum pin with epoxy glue was attached to the black film side. After fixing the pin with a jig, it was heated in an oven heated to 200 ° C. for 5 minutes to fix the pin to the black film. Then, a tensile test was performed with Ez-test manufactured by Shimadzu Corporation to evaluate the film strength.
This item was evaluated based on the following criteria. The measurement is performed 5 times, and the evaluation is performed based on the average value of the measurement results for 3 times excluding the minimum value and the maximum value.
⊚: The value of the tensile test is 320 N or more.
◯: The value of the tensile test is 300 N or more and less than 320 N.
Δ: The value of the tensile test is 280 N or more and less than 300 N.
X: The value of the tensile test is less than 280 N.

According to Examples, (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-shielding material, and (E) an epoxy compound satisfying predetermined conditions. It can be seen that the resin composition containing the above can form a black matrix having high resistance and excellent water resistance, and is excellent in sensitivity. Further, by using such a resin composition, a black matrix having excellent film strength can be formed.
On the other hand, according to Comparative Example 1, it can be seen that when the resin composition does not contain the epoxy compound (E) satisfying a predetermined condition, it is difficult to form a black matrix having excellent water resistance.
Further, according to Comparative Examples 2 and 3, the resin composition contained an acrylic resin such as a styrene-methacrylic acid copolymer or a vinyl group-containing acrylic resin instead of the (E) epoxy compound satisfying a predetermined condition. If so, it can be seen that it is difficult to form a high resistance black matrix. Further, when such a resin composition is used, it is difficult to form a black matrix having excellent film strength.
Further, according to Comparative Example 4, when the resin composition contains a novolak resin instead of the (E) epoxy compound satisfying a predetermined condition, the sensitivity and development of the resin composition can be formed even if a high resistance black matrix can be formed. It can be seen that the solubility in the liquid is inferior.

Claims (11)

A resin composition used to form a black matrix.
(A) Alkali-soluble resin and
(B) Photopolymerizable compound and
(C) Photopolymerization initiator and
(D) Shading material and
(E) Epoxy compound and
Including
The alkali-soluble resin (A) contains a resin containing an aromatic ring in the main chain.
The epoxy compound (E) has the following formula (E1):

(In the formula (E1), OGly is a glycidyloxy group, R ^e1 is a halogen atom or a monovalent group having 1 to 8 carbon atoms, a is an integer of 0 to 4, and b is a parenthesis. number of repetitions of the unit of the inner, when a is an integer of 2 or more, two R ^e1 adjacent on the benzene ring, is bonded to, may form a ring, R ^e2 each other, polycycloalkanes A divalent group obtained by removing two hydrogen atoms from , or the following formula (E1-1):

In a group represented by the formula (E1-1), OGly is glycidyloxy ^{group, R e3} are benzene, naphthalene, anthracene, phenanthrene, and at least one selected from the group consisting of terphenyl It is an aromatic hydrocarbon group, R ^e4 is a halogen atom or an alkyl group having 1 to 4 carbon atoms, c is 0 , d is an integer of 0 to 8, and R ^e5 is a hydrogen atom. Or the following formula (E1-2):

In the formula (E1-2), OGly is a glycidyloxy group, R ^e6 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and e is a group represented by. It is an integer from 0 to 4. )
Contains an epoxy compound represented by
A resin composition having an average molecular weight of 800 or more of the epoxy compound represented by the formula (E1). The resin composition according to claim 1, wherein the alkali-soluble resin (A) contains a resin (a-1) having a cardo structure in its structure. In the formula ^{(E1), R e2} is a divalent group represented by a divalent group formed by removing two hydrogen atoms from a polycycloalkane, or the formula (E1-1), wherein c The resin composition according to claim 1 or 2, wherein is 0 and ^{Re 5 is a group which is a hydrogen atom.} The alkali-soluble resin (A) is a phenol novolac resin (a-2) or a polybasic acid anhydride (a) of a reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b). -3c) The resin composition according to any one of claims 1 to 3, which comprises an adduct (a-3). Am / Em when the total amount (number of moles) of active hydrogen groups contained in the (A) alkali-soluble resin is Am and the total amount (number of moles) of epoxy groups contained in the (E) epoxy compound is Em. The resin composition according to any one of claims 1 to 4, wherein is in the range of 0.25 or more and 4.0 or less. The item according to any one of claims 1 to 5, wherein the content of the epoxy compound represented by the formula (E1) in the total solid content of the resin composition is 0.5% by mass or more and 10% by mass or less. Resin composition. The resin composition according to any one of claims 1 to 6, wherein the light-shielding material (D) contains carbon black. In the cured film obtained by curing the resin composition, the volume resistivity of the cured film is 1.0 × 10 ¹⁰ Ω · cm or more, and the optical density (OD value) of the cured film is 2.5 / μm or more. The resin composition according to any one of claims 1 to 7. A black matrix obtained by curing the resin composition according to any one of claims 1 to 8. A display device including the black matrix according to claim 9. A step of forming a coating film by applying the resin composition according to any one of claims 1 to 8.
A step of regioselectively exposing the coating film and
A step of developing the exposed coating film to form a patterned cured film, and
A method for producing a black matrix, which comprises a step of baking the patterned cured film.