JP7175168B2 - Photosensitive resin composition, method for producing patterned cured film, and patterned cured film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, and a patterned cured film. The present invention also provides a bank made of a cured film of the photosensitive resin composition described above, a bank-equipped substrate for manufacturing an optical element comprising the bank, an optical element comprising the bank-equipped substrate, a display device comprising the optical element, The present invention relates to a bank forming method and an optical element manufacturing method using the photosensitive resin composition described above.

Conventionally, optical elements such as organic EL display elements, color filters, and organic TFT arrays are formed by forming banks (partition walls) surrounding pixels on a substrate, and then forming various functional layers in the area surrounded by the banks. is manufactured by laminating As a method for easily forming such banks, a method of forming banks by photolithography using a photosensitive resin composition is known (Patent Document 1).

Further, as a method of laminating various functional layers in the area surrounded by the banks, there is a method of preparing an ink containing the materials constituting the functional layers and injecting the prepared ink into the area surrounded by the banks. It has been known. In this method, the inkjet method is often adopted because it is easy to accurately inject a predetermined amount of ink into a predetermined location.

Furthermore, when pixels are formed using ink, ink repellency is imparted to the banks in order to prevent the ink from adhering to the banks and to prevent ink injected between adjacent pixels from being mixed. is required. As a method of imparting ink repellency to the bank, for example, a method of incorporating a fluororesin into the bank is known (Patent Document 2).

JP 2010-262940 A WO2008-149498

However, as a result of investigation by the present inventors, when a fluorine-based resin is added to the photosensitive resin composition used for forming the bank for the purpose of imparting ink repellency to the formed bank, the photosensitive resin composition It was confirmed that in a substrate provided with a patterned cured film formed using a material, liquid repellency may be expressed even in a non-patterned area not covered with a photosensitive resin composition.
When this patterned cured film is used as a bank in the above optical element, if liquid repellency occurs in the non-patterned portion as described above, the ink for forming the pixel will be formed in the area surrounded by the bank. There is a problem that a sufficient amount of ink cannot be injected into the area surrounded by the bank because it is repelled inside.

Such a problem is conspicuous when injecting ink into a region surrounded by banks by an inkjet method. In the inkjet method, ink is ejected as droplets from an inkjet head into a region surrounded by banks. This is because it is repelled outside the area where the

The present invention has been made in view of the above problems, and provides a photosensitive resin composition capable of forming a patterned cured film capable of suppressing liquid repellency in a non-pattern area, and a pattern using the photosensitive resin composition. a patterned cured film comprising a cured product of the photosensitive resin composition described above, a bank comprising a cured film of the photosensitive resin composition described above, and an optical system comprising the bank A substrate with a bank for manufacturing an element, an optical element having the substrate with the bank, a display device having the optical element, a method for forming the bank using the photosensitive resin composition described above, and a method for manufacturing the optical element. intended to provide

The present inventors found that in a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a fluororesin (D), N- The inventors have found that the above problems can be solved by using an oxime ester compound having a predetermined structure containing an aromatic group-substituted carbazole skeleton as the photopolymerization initiator (C), and have completed the present invention. More specifically, the present invention provides the following.

（式（Ｃ１）中、Ｘ^０１は、下記式（Ｃ１－１）：

で表される構造において、芳香族環上に結合する水素原子のうち、ｔ２＋ｔ３個の水素原子を除いた基であり、Ｘ^０２及びＸ^０３は、それぞれ独立に１価の有機基であり、Ｘ^０４及びＸ^０５は、それぞれ独立に水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｔ０～ｔ３は、それぞれ独立に、０又は１であり、ｔ２及びｔ３の少なくとも一方は１であり、
式（Ｃ１－１）中、Ｘ^０６は、カルバゾール環中の窒素原子にＣ－Ｎ結合で結合する１価の置換基を有してもよい芳香族基であり、Ｘ^０７及びＸ^０８は、それぞれ独立に、ニトロ基、置換基を有してもよいアロイル基、又は置換基を有してもよいヘテロアロイル基であり、ｔ４及びｔ５は、それぞれ独立に０又は１である。）
で表される光重合開始剤（Ｃ－Ｉ）を含む、感光性樹脂組成物である。 A first aspect of the present invention is a photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a fluororesin (D). and the photopolymerization initiator (C) is represented by the following formula (C1):

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

In the structure represented by, of the hydrogen atoms bonded to the aromatic ring, a group excluding t2 + t3 hydrogen atoms, X ⁰² and X ⁰³ are each independently a monovalent organic group, and X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, and t0 to t3 are each independently 0 or 1, at least one of t2 and t3 is 1;
In formula (C1-1), X ⁰⁶ is an aromatic group optionally having a monovalent substituent bonded to the nitrogen atom in the carbazole ring via a C—N bond, and X ⁰⁷ and X ⁰⁸ are Each independently represents a nitro group, an optionally substituted aroyl group, or an optionally substituted heteroaroyl group, and t4 and t5 are each independently 0 or 1. )
A photosensitive resin composition containing a photopolymerization initiator (C-I) represented by

A second aspect of the present invention is to apply the photosensitive resin composition according to the first aspect on a substrate to form a coating film;
exposing the coating film,
the coating is patterned, or
A method for producing a patterned cured film in which a coating film is subjected to position-selective exposure, and then the exposed coating film is developed.

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

A fourth aspect of the present invention is a bank comprising a cured product of the photosensitive resin composition according to the first aspect, which is used for bank formation.

A fifth aspect of the present invention is a banked substrate for manufacturing an optical element, comprising the bank according to the fourth aspect.

A sixth aspect of the present invention is an optical element comprising the banked substrate for manufacturing the optical element according to the fifth aspect.

A seventh aspect of the present invention is a display device comprising the optical element according to the sixth aspect.

In an eighth aspect of the present invention, the photosensitive resin composition according to the first aspect used for bank formation is applied onto a substrate to form a coating film;
exposing the coating film,
the coating is patterned, or
In this bank forming method, the coating film is subjected to position-selective exposure, and then the exposed coating film is developed.

A ninth aspect of the present invention is a method for manufacturing an optical element, comprising forming pixels by injecting ink into regions surrounded by banks formed on a substrate by the method according to the eighth aspect. be.

According to the present invention, a photosensitive resin composition capable of forming a patterned cured film capable of suppressing liquid repellency in a non-patterned area, a method for producing a patterned cured film using the photosensitive resin composition, A patterned cured film made of a cured product of the aforementioned photosensitive resin composition, a bank made of a cured film of the aforementioned photosensitive resin composition, a banked substrate for manufacturing an optical element comprising the bank, and the It is possible to provide an optical element having a bank-attached substrate, a display device having the optical element, a method for forming a bank using the above-described photosensitive resin composition, and a method for manufacturing an optical element.

<<Photosensitive resin composition>>
A photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a fluororesin (D). The photopolymerization initiator (C) contains an oxime ester compound represented by the following formula (C1) as a photopolymerization initiator (CI).

In formula (C1), X ⁰¹ is a group obtained by removing t2+t3 hydrogen atoms among the hydrogen atoms bonded to the aromatic ring in the structure represented by formula (C1-1) below. X ⁰² and X ⁰³ are each independently a monovalent organic group. X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. t0 to t3 are each independently 0 or 1; At least one of t2 and t3 is 1.

式（Ｃ１－１）中、Ｘ^０６は、カルバゾール環中の窒素原子にＣ－Ｎ結合で結合する１価の置換基を有してもよい芳香族基である。Ｘ^０７及びＸ^０８は、それぞれ独立に、ニトロ基、置換基を有してもよいアロイル基、又は置換基を有してもよいヘテロアロイル基である。ｔ４及びｔ５は、それぞれ独立に０又は１である。

In formula (C1-1), X ⁰⁶ is an aromatic group optionally having a monovalent substituent bonded to the nitrogen atom in the carbazole ring via a C—N bond. X ⁰⁷ and X ⁰⁸ are each independently a nitro group, an optionally substituted aroyl group, or an optionally substituted heteroaroyl group. t4 and t5 are each independently 0 or 1;

The photosensitive resin composition contains a combination of a fluorine-based resin (D) and a photopolymerization initiator (C-I) together with an alkali-soluble resin (A) and a photopolymerizable monomer (B), thereby obtaining a photosensitive resin The composition can be used to form a patterned cured film that can suppress liquid repellency in non-patterned areas.
Such a patterned cured film is suitably used for forming banks for partitioning pixels in color filters, organic EL display elements, quantum dot displays, organic TFT arrays, or the like. This is because by suppressing the lyophobicity in the area surrounded by the bank, it is difficult to cause an ink injection failure in which the ink is repelled when injecting the ink for pixel formation into the area surrounded by the bank. be.

In addition, when the above photosensitive resin composition is used, ink for forming pixels is prevented from penetrating adjacent pixel regions when banks are formed by a photolithographic method including position-selective exposure and development. It is easy to achieve both a sufficient function as a partition wall for the purpose and desirable light transmittance.

The essential or optional components contained in the photosensitive resin composition and the method for producing the photosensitive resin composition will be described below in order.

<Alkali-soluble resin (A)>
The photosensitive resin composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) is not particularly limited, and can be appropriately selected from alkali-soluble resins conventionally blended in various photosensitive resin compositions.
Here, in this specification, the alkali-soluble resin (A) refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) that imparts alkali-solubility in the molecule.

Resins suitable as the alkali-soluble resin (A) include a resin (a-1) having a cardo structure (hereinafter also referred to as "cardo resin (a-1)").
When the resin (a-1) having a cardo structure is used as the alkali-soluble resin, it is easy to obtain a photosensitive resin composition having excellent resolution, and the photosensitive resin composition is used to form a cured film that does not flow excessively when heated. Easy to form. Therefore, it is easy to form a cured film having a good shape.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings, since a photosensitive resin composition having an excellent balance between sensitivity and developability can be easily obtained. In addition, the polybasic acid anhydride (a-3c) contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2). is more preferred.

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

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

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

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

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

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

Moreover, the organic group as R ^a10 may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, or an oxetanyl group.
An acyl group having an unsaturated double bond such as an acryloyloxy group or a methacryloyloxy group is, for example, at least part of the epoxy group in the acrylic resin (a-4) containing a structural unit having an epoxy group, It can be produced by reacting an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.
Alternatively, by reacting a structural unit derived from an unsaturated carboxylic acid such as acrylic acid or methacrylic acid in the acrylic resin (a-4) with a compound having an epoxy group and an unsaturated double bond, , an unsaturated double bond can be introduced into the acrylic resin (a-4). Examples of compounds having an epoxy group and an unsaturated double bond include glycidyl (meth)acrylate and compounds represented by formulas (a-4-1a) to (a-4-1o) described later. can be done.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

When the acrylic resin (a-4) has a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the acrylic resin (a-4) is It is preferably 1 mol % or more and 50 mol % or less, more preferably 1 mol % or more and 30 mol % or more, and particularly preferably 1 mol % or more and 20 mol % or less, relative to the number of moles of all structural units of -4).
Since the acrylic resin (a-4) contains a structural unit having an unsaturated double bond in an amount within the above range, the acrylic resin can be incorporated into the cross-linking reaction in the resist film for uniformity. It is effective in improving the heat resistance and mechanical properties of

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

The content of the alkali-soluble resin (A) is 20% by mass or more and 85% by mass or less with respect to the mass (total solid content) of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. It is preferably 25% by mass or more and 75% by mass or less. By setting it as said range, it is easy to obtain the photosensitive resin composition which is excellent in developability.

<Photopolymerizable Monomer (B)>
As the photopolymerizable monomer (B), a monomer having an ethylenically unsaturated group can be preferably used. The monomers having ethylenically unsaturated groups include monofunctional monomers and polyfunctional monomers.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol ( meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(meth) acryloyloxy-2-hydroxypropyl phthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 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. These monofunctional monomers can be used singly or in combination of two or more.

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

Among these monomers having an ethylenically unsaturated group, the adhesiveness of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing tend to increase. is preferred, polyfunctional monomers having tetrafunctional or higher functionality are more preferred, and polyfunctional monomers having pentafunctional or higher functionality are even more preferred.

The content of the photopolymerizable monomer (B) in the photosensitive resin composition is 1% by mass or more with respect to the mass of the photosensitive resin composition (total solid content) excluding the mass of the organic solvent (S) described later. 50 mass % or less is preferable, and 5 mass % or more and 40 mass % or less is more preferable. By setting the amount within the above range, there is a tendency that sensitivity, developability, and resolution are easily balanced.

<Photoinitiator (C)>
The photosensitive resin composition contains a photopolymerization initiator (CI) represented by the following formula (C1) as the photopolymerization initiator (C).

In formula (C1), X ⁰¹ is a group obtained by removing t2+t3 hydrogen atoms among the hydrogen atoms bonded to the aromatic ring in the structure represented by formula (C1-1) below. X ⁰² and X ⁰³ are each independently a monovalent organic group. X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. t0 to t3 are each independently 0 or 1, and at least one of t2 and t3 is 1;

In formula (C1-1), X ⁰⁶ is an aromatic group optionally having a monovalent substituent bonded to the nitrogen atom in the carbazole ring via a C—N bond. X ⁰⁷ and X ⁰⁸ are each independently a nitro group, an optionally substituted aroyl group, or an optionally substituted heteroaroyl group. t4 and t5 are each independently 0 or 1;

In formula (C1-1), X ⁰⁶ is an aromatic group optionally having a monovalent substituent bonded to the nitrogen atom in the carbazole ring via a C—N bond. The aromatic group may be an aryl group or a heteroaryl group. The heteroatom possessed by the heteroaryl group includes O, S, N, P, Si and the like.

The number of carbon atoms in the optionally substituted aromatic group as X ⁰⁶ is not particularly limited. The number of carbon atoms in the optionally substituted aromatic group as X ⁰⁶ is, for example, preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and particularly preferably 1 or more and 20 or less. The number of carbon atoms of the aromatic group which may have a substituent does not include the number of carbon atoms of the substituent.

Heterocyclic rings constituting the heteroaryl group as X ⁰⁶ include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, tetrazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran , benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline.

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

The aromatic group as X ⁰⁶ may have a substituent. Examples of the substituent that the aromatic group represented by X ⁰⁶ may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to 10 carbon atoms. cycloalkyl group, cycloalkoxy group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, 2 to 20 carbon atoms saturated aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group , an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, having a substituent naphthyl group optionally having substituents, naphthoxy group optionally having substituents, naphthoyl group optionally having substituents, naphthoxycarbonyl group optionally having substituents, naphtho optionally having substituents an yloxy group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, an amino group, Examples thereof include amino group, morpholin-1-yl group and piperazin-1-yl group substituted with one or two organic groups, halogen, nitro group and cyano group.
The number of substituents that the aromatic group as X ⁰⁶ may have is not particularly limited, and may be one or more than two. When the aromatic group as X ⁰⁶ has multiple substituents, the multiple substituents may be the same or different.

Among the above groups as X ⁰⁶ , an aryl group is preferable from the viewpoint of ease of synthesis and availability of the photopolymerization initiator (C-I), and a phenyl group, a naphthalene-1-yl group, and a naphthalene-2- An yl group is more preferred, and a phenyl group is particularly preferred.

In formula (C1-1), X ⁰⁷ and X ⁰⁸ are each independently a nitro group, an optionally substituted aroyl group, or an optionally substituted heteroaroyl group.

The number of carbon atoms in the aryl group contained in the aroyl group is, for example, preferably 6 or more and 50 or less, more preferably 6 or more and 30 or less, and particularly preferably 6 or more and 20 or less. When the aryl group contained in the aroyl group has a substituent, the above number of carbon atoms in the aryl group does not include the number of carbon atoms in the substituent.
Preferable examples of the aryl group contained in the aroyl group include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 2-phenylphenyl group, a 3-phenylphenyl group and a 4-phenylphenyl group. mentioned.

The heteroaryl group contained in the heteroaroyl group preferably has, for example, 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms. When the heteroaryl group contained in the aroyl group has a substituent, the number of carbon atoms in the heteroaryl group does not include the number of carbon atoms in the substituent.
Preferable examples of the heterocyclic ring constituting the heteroaryl group contained in the heteroaroyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, tetrazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like.
A bond possessed by the heteroaryl group may be bonded to a carbon atom constituting the above heterocyclic ring, or may be bonded to a heteroatom constituting the above heterocyclic ring.

The substituents which the aroyl group which may have a substituent and the heteroaroyl group which may have a substituent may have are the same as the substituents which the aromatic group as X ⁰⁶ may have. be.
The number of substituents that the aroyl group optionally having a substituent and the heteroaroyl group optionally having a substituent may have is not particularly limited, and may be 1 or 2 or more. good too. When the optionally substituted aroyl group and the optionally substituted heteroaroyl group have multiple substituents, the multiple substituents may be the same or different.

Preferable specific examples of the optionally substituted aroyl group and the optionally substituted heteroaroyl group include a benzoyl group, a 2-methylbenzoyl group, a 3-methylbenzoyl group and a 4-methylbenzoyl group. , 2,3-dimethylbenzoyl group, 2,4-dimethylbenzoyl group, 2,5-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 3,4-dimethylbenzoyl group, 3,5-dimethylbenzoyl group, 2 -methoxybenzoyl group, 3-methoxybenzoyl group, 4-methoxybenzoyl group, 2,3-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 3 , 4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 2-chlorobenzoyl group, 3-chlorobenzoyl group, 4-chlorobenzoyl group, 2,3-dichlorobenzoyl group, 2,4-dichlorobenzoyl group, 2 ,5-dichlorobenzoyl group, 2,6-dichlorobenzoyl group, 3,4-dichlorobenzoyl group, 3,5-dichlorobenzoyl group, 2-(9H-carbazol-9-yl)benzoyl group, 3-(9H- carbazol-9-yl)benzoyl group, 4-(9H-carbazol-9-yl)benzoyl group, thiophen-2-ylcarbonyl group, furan-2-ylcarbonyl group, pyrrol-2-ylcarbonyl group, benzothiophene- 2-ylcarbonyl group, benzofuran-2-ylcarbonyl group, and indol-2-ylcarbonyl group.

X ⁰¹ is not particularly limited as long as it is a group obtained by removing t2+t3 hydrogen atoms among the hydrogen atoms bonded to the aromatic ring in the structure represented by the above formula (C1-1). As the group represented by the above formula (C1-1), monovalent or divalent groups represented by the following formulas (C1-1a) to (C1-1c) are preferable.

In formulas (C1-1a) to (C1-c), t4, t5, and X ⁰⁶ , X ⁰⁷ and X ⁰⁸ are the same as in formula (C1-1). X ⁰⁹ is a divalent aromatic group attached via a C—N bond to the nitrogen atom in the carbazole ring. Of the two bonds of X ⁰⁹ , the other of the bonds that bind to the carbazole ring in formulas (C1-1a) and (C1-1c) constitutes an aromatic ring contained in X ⁰⁹ . bond to the carbon atom that
X ⁰⁷ corresponds to a divalent group obtained by removing one hydrogen atom bonded to the aromatic ring from the above-mentioned monovalent organic group containing an aromatic ring as X ⁰⁶ .

As described above, the aromatic group for X ⁰⁶ is preferably an aryl group, more preferably a phenyl group, a naphthalen-1-yl group and a naphthalen-2-yl group, and particularly preferably a phenyl group.
Therefore, X ⁰⁹ includes phenylene groups such as o-phenylene group, m-phenylene group and p-phenylene group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1 ,2-diyl group, naphthalene-1,4-diyl group and naphthalene-1,6-diyl group are preferred, and phenylene groups such as o-phenylene group, m-phenylene group and p-phenylene group are preferred. groups are more preferred, and p-phenylene groups are particularly preferred.

In formulas (C1-1a) to (C1-1c), the bonding positions of X ⁰⁷ and X ⁰⁸ on the carbazole ring are not particularly limited.
From the viewpoint of ease of synthesis and availability of the compound represented by formula (C1), the group represented by formula (C1-1a), the group represented by (C1-1b), and the formula (C1-1c) ) Preferred examples of the group represented by the formula (C1-1aa), the group represented by the formula (C1-1ba), and the group represented by the formula (C1-1ca) is mentioned.

In formula (C1), X ⁰² and X ⁰³ are each independently a monovalent organic group. Examples of suitable organic groups for X ⁰² and X ⁰³ include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents. optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, substituted a naphthoxycarbonyl group optionally having a group, a naphthoyloxy group optionally having a substituent, a naphthylalkyl group optionally having a substituent, a heterocyclyl group optionally having a substituent, a substituent an amino group substituted with 1 or 2 organic groups, an alkyl group substituted with an amino group, an amino group substituted with 1 or 2 organic groups An alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, and the like.

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

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

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

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

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

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

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

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

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

When X ⁰² and X ⁰³ are an alkyl group substituted with an amino group and an alkyl group substituted with an amino group substituted with 1 or 2 organic groups, when X ⁰² and X ⁰³ are an alkyl group is preferably an amino group or an amino group substituted with one or two organic groups.
Preferable specific examples of an alkyl group substituted with an amino group and an alkyl group substituted with an amino group substituted with one or two organic groups include a 2-aminoethyl group and 3-amino-n-propyl group, 2-amino-n-propyl group, 4-amino-n-butyl group, 2-(N,N-dimethylamino)ethyl group, 3-(N,N-dimethylamino)-n-propyl group, 2 -(N,N-dimethylamino)-n-propyl group, 4-(N,N-dimethylamino)-n-butyl group, 2-(N,N-diethylamino)ethyl group, 3-(N,N- diethylamino)-n-propyl group, 2-(N,N-diethylamino)-n-propyl group, 4-(N,N-diethylamino)-n-butyl group, 2-(N-acetyl-N-acetoxyamino) ethyl group, 3-(N-acetyl-N-acetoxyamino)-n-propyl group, 2-(N-acetyl-N-acetoxyamino)-n-propyl group, and 4-(N-acetyl-N-acetoxy amino)-n-butyl group.

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

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

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

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

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

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

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

Preferable examples of A ² include 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. Preferred specific examples of ^A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl. phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl groups.

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

式（Ｃ１ａ）及び（Ｃ１ｂ）中、Ｘ^０１０及びＸ^０１１はそれぞれ有機基である。ｔ６は０以上４以下の整数である。Ｘ^０１０及びＸ^０１１がベンゼン環上の隣接する位置に存在する場合、Ｘ^０１０及びＸ^０１１が互いに結合して環を形成してもよい。ｔ７は１以上８以下の整数である。ｔ８は１以上５以下の整数である。ｔ９は０以上（ｔ８＋３）以下の整数である。Ｘ^０１２は有機基である。 X ^{02 and X 03 have been described above, and X 02 and X 03 are preferably} groups represented by the following formula (C1a) or (C1b).

In formulas (C1a) and (C1b), X ⁰¹⁰ and X ⁰¹¹ are each organic groups. t6 is an integer of 0 or more and 4 or less. When X ⁰¹⁰ and X ⁰¹¹ are present at adjacent positions on the benzene ring, X ⁰¹⁰ and X ⁰¹¹ may combine with each other to form a ring. t7 is an integer of 1 or more and 8 or less. t8 is an integer of 1 or more and 5 or less. t9 is an integer from 0 to (t8+3). X ⁰¹² is an organic group.

Examples of organic groups for X ⁰¹⁰ and X ⁰¹¹ in formula (C1a) are the same as for X ⁰² and X ⁰³ . X ⁰¹⁰ is preferably an alkyl group or a phenyl group. When X ⁰¹⁰ 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, X ⁰¹⁰ is most preferably a methyl group. When X ⁰¹⁰ and X ⁰¹¹ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by formula (C1a) in which X ⁰¹⁰ and X ⁰¹¹ form a ring include naphthalen-1-yl group and 1,2,3,4-tetrahydro naphthalene-5-yl group and the like. In the above formula (C1a), t6 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In formula (C1b) above, X ⁰¹² is an organic group. Examples of the organic group include groups similar to the organic groups described for X ⁰² and X ⁰³ . Among organic groups, alkyl groups are preferred. Alkyl groups may be straight or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. X ⁰¹² is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.

In formula (C1b), t8 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the formula (C1b), t9 is 0 or more and (t8+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0. In formula (C1b), t7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (C1), X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. be. A phenyl group, a naphthyl group and the like are preferably exemplified as substituents which may be possessed when X ⁰⁴ and X ⁰⁵ are alkyl groups. In addition, when X ⁰⁴ and X ⁰⁵ are aryl groups, the substituents which may be present include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and the like. are preferably exemplified.

In formula (C1), X ⁰⁴ and X ⁰⁵ are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like. Preferred examples are, among these, a methyl group or a phenyl group is more preferred.

Regarding the oxime ester compound represented by the formula (C1) described above, since it is easy to form a patterned cured film having a good cross-sectional shape, the sum of t2 and t3 is 1, and the sum of t4 and t5 is 1. Preferably the sum is 1 or 2.

As described above, X ⁰¹ is preferably a group represented by formula (C1-1aa), a group represented by formula (C1-1ba), or a group represented by formula (C1-1ca).
Preferable specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1aa) include the following compounds.

Preferable specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1ba) include the following compounds.

Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1ca) include the following compounds.

<Photoinitiator (C-II)>
The photosensitive resin composition includes, as the photopolymerization initiator (C), the photopolymerization initiator (C-II) described above, and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I). ) may be included. The other photopolymerization initiator (C-II) is not particularly limited as long as it is a photopolymerization initiator that does not correspond to the photopolymerization initiator (C-I).

Preferred examples of the photopolymerization initiator (C-II) include an oxime ester compound having a structure that does not correspond to the above formula (C1); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane -1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butane-1 -one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl α-Aminoketone compounds such as -1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc. ; 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone and other α-hydroxyketone photopolymerization initiators; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl methyl ketal and other benzoin photoinitiators Photopolymerization initiator; benzophenone such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4'-methyldiphenylsulfide, 4,4'-bisdiethylaminobenzophenone thioxanthone-based photopolymerization initiators; thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-s-triazine, 2- Phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-pipenyl-4.6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-( naphth-1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6 -triazine, 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine, 2-[4-(4-methoxystyryl)phenyl]-4,6-bis(trichloromethyl)-1,3, Triazine-based photopolymerization initiators such as 5-triazine; carbazole-based photopolymerization initiators; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)- 1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole, 2,2'-bis(2-bromophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl )-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′ Biimidazole-based photopolymerization initiators such as -tetraphenyl-1,2'-biimidazole; and benzimidazoline-based photopolymerization initiators represented by the following formula are exemplified.

The mass ratio of the photopolymerization initiator (CI) to the mass of the photopolymerization initiator (C) is not particularly limited as long as the object of the present invention is not impaired. The ratio of the mass of the photopolymerization initiator (C-I) to the mass of the photopolymerization initiator (C) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90 % by mass or more is even more preferred, and 100% by mass is particularly preferred.

The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 30% by mass or less with respect to the total mass of the solid content of the photosensitive resin composition, and 0.5% by mass or more and 20% by mass or less. more preferred. By setting the content of the photopolymerization initiator (C) within the above range, it is possible to obtain a photosensitive resin composition that has good curability and is less likely to cause defects in pattern shape.

<Fluorine resin (D)>
The photosensitive resin composition contains a fluororesin (D). When the fluorine-based resin (D) is contained in the photosensitive resin composition, the photosensitive resin composition is used when forming pixels using ink in a color filter, an organic EL display element, a quantum dot display, an organic TFT array, or the like. A bank formed by an object tends to repel ink. As a result, it is possible to prevent ink from adhering to the bank and from mixing ink with adjacent pixels when ink is injected into a region surrounded by the bank.

The fluororesin (D) is not particularly limited as long as it is a resin containing a fluorine atom and capable of imparting ink repellency to various inks to a bank formed using a photosensitive resin composition. The fluororesin (D) may be a homopolymer of a fluorine atom-containing monomer, or a copolymer of a fluorine atom-containing monomer and a fluorine atom-free monomer.

Preferred examples of the fluororesin (D) include a copolymer obtained by copolymerizing at least (d1) a monomer having an ethylenically unsaturated group and a fluorine atom and (d2) (meth)acrylic acid. . When such a fluororesin (D) is used, it is easy to form a bank excellent in liquid repellency to ink for pixel formation using a photosensitive resin composition.

[(d1) Monomer Having Ethylenically Unsaturated Group and Fluorine Atom]
A monomer having an ethylenically unsaturated group and a fluorine atom (hereinafter also referred to as "(d1) monomer") is not particularly limited as long as it has an ethylenically unsaturated group and a fluorine atom. Examples of such a (d1) monomer include compounds represented by the following formula (d1-1). These (d1) monomers can be used singly or in combination of two or more.

In formula (d1-1), X ¹ and X ² are each independently a hydrogen atom or a fluorine atom. X3 is a hydrogen atom ^, a fluorine atom, a methyl group, or a perfluoromethyl group. ^X4 and ^X5 are each independently a hydrogen atom, a fluorine atom, or a perfluoromethyl group. Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond. a is an integer of 0 or more and 3 or less. b and c are each independently 0 or 1;

When Rf is a fluorine-containing alkyl group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 3 or more and 10 or less, and particularly preferably 4 or more and 6 or less. When Rf is a fluorine-containing alkyl group having an ether bond, the number of carbon atoms is preferably 2 or more and 50 or less, more preferably 3 or more and 20 or less, and particularly preferably 4 or more and 6 or less.

(d1) The content of structural units derived from a monomer is preferably 30 mol% or more and 80 mol% or less, and 40 mol% or more and 60 mol% or less, based on the number of moles of all structural units of the fluororesin (D). is more preferred. When the content of the structural unit derived from the (d1) monomer in the fluororesin (D) is within the above range, it is easy to form a bank with excellent ink repellency using the photosensitive resin composition, and the photosensitive resin composition The compatibility between the fluororesin (D) and other components in the resin composition tends to be good.

The (d1) monomer preferably has a group represented by —(CF ₂ ) _t F. t is an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 8 or less, and still more preferably an integer of 2 or more and 6 or less. When the (d1) monomer has the above group, it is easy to form a bank having excellent ink repellency using the photosensitive resin composition.

[(d2) (meth) acrylic acid]
The fluororesin (D) preferably contains structural units derived from (d2) (meth)acrylic acid, which is a monomer having a carboxy group, in order to improve the developability of the photosensitive resin composition.

(d2) The content of structural units derived from (meth)acrylic acid is preferably 0.1 mol % or more and 20 mol % or less based on the number of moles of all structural units of the fluororesin (D). When the content of (d2) the structural unit derived from (meth)acrylic acid in the fluororesin (D) is within the above range, the developability is good and the photosensitivity is such that a bank with excellent ink repellency can be formed. It is easy to obtain a resin composition.

If necessary, the fluororesin (D) may be copolymerized with monomers other than the above monomers (d1) and (d2). Such other monomers include the various monomers described below.

[(d3) a monomer having an ethylenically unsaturated group and an epoxy group]
The fluororesin (D) is preferably a copolymer obtained by further copolymerizing a monomer having an ethylenically unsaturated group and an epoxy group (hereinafter also referred to as "(d3) monomer"). By copolymerizing the (d3) monomer, the ink repellency of the bank formed from the photosensitive resin composition can be further improved.

(d3) As the monomer, glycidyl (meth)acrylate, an alicyclic epoxy compound represented by the following formulas (d3-1) to (d3-3), a carboxy group of (meth)acrylic acid and a difunctional or higher Monomers obtained by reacting epoxy groups of epoxy compounds, monomers obtained by reacting hydroxyl groups or carboxyl groups of acrylic monomers having hydroxyl groups or carboxyl groups in side chains with epoxy groups of difunctional or higher epoxy compounds, etc. is mentioned. Among them, glycidyl (meth)acrylate is preferred. These (d3) monomers can be used singly or in combination of two or more.

In formulas (d3-2) and (d3-3), R ^1d is a hydrogen atom or a methyl group. u is an integer of 1 or more and 10 or less. v and w are each independently an integer of 1 or more and 3;

When the fluororesin contains a structural unit derived from the (d3) monomer, the content of the structural unit in the fluororesin (D) is 1 per mole of all structural units of the fluororesin (D). mol % or more and 40 mol % or less is preferable, and 5 mol % or more and 15 mol % or less is more preferable. When the content of the structural unit derived from the (d3) monomer in the fluororesin (D) is within the above range, it is easy to obtain a photosensitive resin composition capable of forming a bank with good ink repellency.

[(d4) a monomer having a structure represented by formula (d4-1)]
The fluororesin (D) is a copolymer obtained by copolymerizing an ethylenically unsaturated group and a monomer having a structure represented by the following formula (d4-1) (hereinafter also referred to as "(d4) monomer"). Polymers are preferred. By copolymerizing the (d4) monomer, it is easy to obtain a photosensitive resin composition with excellent developability, and the compatibility between the fluororesin (D) and other components in the photosensitive resin composition can be improved. .

The (d4) monomer more preferably has an ethylenically unsaturated group and a structure represented by the following formula (d4-2).

In formulas (d4-1) and (d4-2), R ^2d is an alkylene group having 1 to 5 carbon atoms. The alkylene group may be linear or branched. As the alkylene group, an alkylene group having 1 or more and 3 or less carbon atoms is preferable, and an ethylene group is most preferable. R ^3d is a hydrogen atom, a hydroxyl group, or an optionally substituted alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is most preferable. Examples of the substituent include a carboxy group, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, and the like. x is an integer of 1 or more. As x, an integer of 1 or more and 60 or less is preferable, and an integer of 1 or more and 12 or less is more preferable.

Examples of such a (d4) monomer include compounds represented by the following formula (d4-3). These (d4) monomers can be used singly or in combination of two or more.

In formula (d4-3), ^R4d is a hydrogen atom or a methyl group. R ^2d , R ^3d and x have the same meanings as in formulas (d4-1) and (d4-2) above.

(d4) The content of structural units derived from a monomer is preferably 1 mol% or more and 40 mol% or less, and may be 5 mol% or more and as much as 25%, based on the number of moles of all structural units in the fluororesin (D). The following are more preferred. (d4) When the content of the structural unit derived from the monomer is within the above range, the developability of the photosensitive resin composition and the relationship between (D) the fluororesin and other components in the photosensitive resin composition Compatibility tends to be good.

[(d5) a monomer having a silicon atom]
The fluororesin (D) is preferably a copolymer obtained by further copolymerizing a monomer having a silicon atom (hereinafter also referred to as "(d5) monomer"). The (d5) monomer is not particularly limited as long as it has an ethylenically unsaturated group and at least one alkoxy group bonded to a silicon atom. By copolymerizing the (d5) monomer, the ink repellency of the bank formed from the photosensitive resin composition can be further improved.

Examples of such a (d5) monomer include compounds represented by the following formula (d5-1). These (d5) monomers can be used alone or in combination of two or more.

In formula (d5-1), R ^5d is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. R ^6d is an alkylene group or a phenylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. R ^7d and R ^8d are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, preferably an alkyl group having 1 to 3 carbon atoms. When multiple ^R7d 's are bound to Si, the multiple ^R7d 's may be the same or different. When multiple (OR ^8d ) are bonded to Si, the multiple (OR ^8d ) may be the same or different. p is 0 or 1, preferably 1; q is an integer of 1 to 3, preferably 2 or 3, more preferably 3;

(d5) The content of structural units derived from a monomer is preferably 20 mol% or less, more preferably 10 mol% or less, relative to the number of moles of all structural units in the fluororesin (D). (d5) When the content of the structural unit derived from the monomer is within the above range, ink repellency and compatibility with other components of the colored photosensitive resin composition tend to be good.

As monomers other than the above monomers, various monomers having an ethylenically unsaturated group can be used, among which acrylic monomers are preferred. Preferred examples of acrylic monomers include 2-hydroxyethyl methacrylate (HEMA), N-hydroxymethyl acrylamide (N-MAA), methyl methacrylate (MAA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBMA) and the like. mentioned. The content of structural units derived from these other monomers in the fluororesin (D) is preferably 0 mol % or more and 25 mol % or less relative to the number of moles of all structural units in the fluororesin (D).

As a method for obtaining a copolymer by reacting the (d1) monomer, the (d2) monomer, and optionally other monomers, a known method can be used.

The weight average molecular weight of the fluororesin (D) is preferably 2,000 or more and 50,000 or less, more preferably 5,000 or more and 20,000 or less. When the weight average molecular weight of the fluororesin (D) is 2,000 or more, the heat resistance and strength of the bank formed using the photosensitive resin composition can be improved. When the weight average molecular weight of the fluororesin (D) is 50,000 or less, the developability of the photosensitive resin composition can be enhanced.

The content of the fluorine-based resin (D) in the photosensitive resin composition is preferably 0.1% by mass or more and 10% by mass, and 0.2% by mass or more and 5% by mass, based on the solid content of the photosensitive resin composition. The following are more preferred. When the photosensitive resin composition contains the fluorine-based resin (D) in such an amount, the photosensitive resin composition can be provided with excellent sensitivity, developability, and resolution, and the photosensitive resin composition It is easy to impart good ink repellency to the ink for forming pixels to the bank formed using

<Colorant (E)>
The photosensitive resin composition may further contain a coloring agent (E). By containing the colorant (E), the photosensitive resin composition is preferably used for forming a colored film such as RGB in a color filter of a liquid crystal display. Moreover, the photosensitive resin composition preferably contains a light shielding agent (E1) as a coloring agent (E). By using the light-shielding agent (E1), a light-shielding bank that partitions pixels in a color filter, an organic EL display element, a quantum dot display, an organic TFT array, or the like can be formed. In addition, in the present application, a bank includes a black matrix that constitutes a color filter in a liquid crystal display.

The coloring agent (E) contained in the photosensitive resin composition is not particularly limited. It is preferable to use the compounds having the following color index (C.I.) numbers.

Examples of yellow pigments that can be suitably used include C.I. I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same and only the number is described.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 , 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 , 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 , and 185.

Examples of orange pigments that can be preferably used include C.I. I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same and only the number is described.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 , 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of purple pigments that can be preferably used include C.I. I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the number is described.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50 mentioned.

Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only the number is described.) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49: 1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64: 1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be preferably used include C.I. I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and only the number is described.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64 , and 66.

Examples of pigments of other hues that can be preferably used include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28 and other brown pigments, C.I. I. Pigment Black 1, C.I. I. Black pigments such as Pigment Black 7 can be used.

Moreover, when providing a light-shielding property to the photosensitive resin composition, it is preferable that the photosensitive resin composition contains a black pigment as a light-shielding agent (E1). A photosensitive resin composition containing a black pigment is suitably used to form a black matrix or black column spacer in a liquid crystal display panel, or to form a bank for partitioning a light-emitting layer in an organic EL element.

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, whether organic or inorganic, such as metal sulfates or metal carbonates, can be used. Among these black pigments, carbon black is preferable because it is easily available and can easily 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 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, but it is preferable to use channel black which has excellent light shielding properties. Resin-coated carbon black may also be used.

Resin-coated carbon black has lower conductivity than carbon black without resin coating, so when used as a black matrix for a liquid crystal display element such as a liquid crystal display, there is little current leakage, and it is a highly reliable low-power. Power consumption displays can be manufactured.

As the carbon black, carbon black that has been subjected to a treatment for introducing acidic groups is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity according to Bronsted's definition. Specific examples of acidic groups include a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like. The acidic groups introduced into carbon black may form a salt. The cation that forms a salt with an acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of cations include various metal ions, cations of nitrogen-containing compounds, ammonium ions, etc. Alkali metal ions such as sodium ions, potassium ions and lithium ions, and ammonium ions are preferred.

Among the carbon blacks that have been treated to introduce acidic groups as described above, carboxylic acid groups, carboxylic acid Carbon blacks having one or more functional groups selected from the group consisting of bases, sulfonic acid groups, and sulfonic acid groups are preferred.

The method for introducing acidic groups into carbon black is not particularly limited. Examples of methods for introducing acidic groups include the following methods.
1) A method of introducing sulfonic acid groups into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using a sulfite, hydrogen sulfite, or the like.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protective group with carbon black having a hydroxyl group.
5) A method of subjecting carbon black to a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group, followed by deprotection.

Among these methods, method 2) is preferable because the treatment for introducing an acidic group is easy and safe. The organic compound having an amino group and an acidic group used in method 2) is preferably a compound in which an amino group and an acidic group are bonded to an aromatic group. 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 acidic groups introduced into carbon black is preferably 1 mmol or more and 200 mmol or less, more preferably 5 mmol or more and 100 mmol or less, relative to 100 g of carbon black.

Carbon black into which acidic groups have been introduced may be coated with a resin.
When a photosensitive 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 resin coating treatment does not particularly affect the dielectric constant of the light-shielding cured film formed using the photosensitive resin composition. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallylphthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins; Thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone. The coating amount of the resin with respect to the carbon black is preferably 1% by mass or more and 30% by mass or less with respect to the total mass of the carbon black and the resin.

Perylene-based pigments can also be preferably used as black pigments. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (e-1), a perylene-based pigment represented by the following formula (e-2), and a perylene-based pigment represented by the following formula (e-3). and perylene pigments. Commercially available products such as K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33 and 34 can be preferably used as perylene pigments.

式（ｅ－１）中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に炭素原子数１以上３以下のアルキレン基を表し、Ｒ^ｅ３及びＲ^ｅ４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 (e-1), R ^e1 and R ^e2 each independently represent an alkylene group having 1 to 3 carbon atoms, R ^e3 and R ^e4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or represents an acetyl group.

式（ｅ－２）中、Ｒ^ｅ５及びＲ^ｅ６は、それぞれ独立に、炭素原子数１以上７以下のアルキレン基を表す。

In formula (e-2), R ^e5 and R ^e6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｅ－３）中、Ｒ^ｅ７及びＲ^ｅ８は、それぞれ独立に、水素原子、炭素原子数１以上２２以下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^ｅ７及びＲ^ｅ８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 (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms and containing a heteroatom of N, O, S or P; good too. When R ^e7 and R ^e8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above formula (e-1), the compound represented by the formula (e-2), and the compound represented by the formula (e-3) are disclosed, for example, in JP-A-62-1753. , and can be synthesized using the method described in JP-B-63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials and subjected to a heating reaction in water or an organic solvent. The desired product can be obtained by reprecipitating the resulting crude product in sulfuric acid, or by recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

In order to disperse the perylene pigment well in the photosensitive resin composition, the average particle size of the perylene pigment is preferably 10 nm or more and 1000 nm or less.

A lactam pigment may also be included as the light shielding agent (E1). Examples of lactam pigments include compounds represented by the following formula (e-4).

In formula (e-4), X ^e represents a double bond and is each independently an E or Z isomer as a geometric isomer, and R ^e9 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, bromine atom, chlorine atom, fluorine atom, carboxy group, or sulfo group; R ^e10 each independently represents a hydrogen atom, methyl group, or phenyl group; R ^e11 each independently represents a hydrogen atom , a methyl group, or a chlorine atom.
The compounds represented by formula (e-4) can be used alone or in combination of two or more.
R ^e9 is preferably bonded to the 6-position of the dihydroindolone ring, and R ^e11 is bonded to the 4-position of the dihydroindolone ring, because the compound represented by formula (e-4) can be easily produced. preferably. From the same point of view, R ^e9 , R ^e10 and R ^e11 are preferably hydrogen atoms.
The compound represented by formula (e-4) has EE isomer, ZZ isomer, and EZ isomer as geometric isomers. may be a mixture of
The compound represented by formula (e-4) can be produced, for example, by the methods described in WO2000/24736 and WO2010/081624.

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

Furthermore, fine particles containing a silver-tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as black pigments. The AgSn alloy fine particles may contain AgSn alloy as a main component, and may contain other metal components such as Ni, Pd, and Au.
The average particle size of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x for obtaining a chemically stable AgSn alloy is 1 ≤ x ≤ 10, and the range of x for simultaneously obtaining chemical stability and blackness is 3≤x≤4.
Here, when the mass ratio of Ag in the AgSn alloy is obtained within the above range of x,
Ag/AgSn=0.4762 when x=1
When x=3, 3Ag/Ag3Sn=0.7317
When x=4, 4·Ag/Ag4Sn=0.7843
When x=10, 10Ag/Ag10Sn=0.9008
becomes.
Therefore, this AgSn alloy becomes chemically stable when it contains 47.6% by mass or more and 90% by mass or less of Ag, and when it contains 73.17% by mass or more and 78.43% by mass or less of Ag Chemical stability and blackness can be obtained effectively with respect to the amount.

This AgSn alloy fine particle can be produced using a normal fine particle synthesis method. Examples of fine particle synthesis methods include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

Although the AgSn alloy fine particles have a high insulating property, depending on the application of the photosensitive resin composition, the surface thereof may be covered with an insulating film in order to further improve the insulating property. A metal oxide or an organic polymer compound is suitable as a material for such an insulating film.
As metal oxides, metal oxides having insulating properties, such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), etc., are preferably used. be done.
As the organic polymer compound, insulating resins such as polyimide, polyether, polyacrylate, and polyamine compounds are preferably used.

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

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

A black composition containing a combination of two or more black or chromatic pigments and/or dyes can be used together with the black pigment described above or in place of the black pigment.
The content of carbon black in the black composition is preferably 3% by mass or less. By using a black composition having a carbon black content of 3% by mass or less, it is easy to suppress the generation of floating matter and development residues after development.
The content of carbon black in the black composition is more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0% by mass.

The hues of the pigments and dyes contained in the black composition are not particularly limited. The black composition may contain black pigments and/or dyes. The black composition may be a combination of multiple black colorants. In this case, for example, perylene black, aniline black, black azo compounds, and the like can be used as the black colorant.
The black composition may contain a combination of two or more pigments and/or dyes having hues other than black so that the composition exhibits a black color.

Since it is possible to finely adjust the hue of black and it is easy to suppress the generation of floating matter and development residues after development, the black composition is more preferable than a coloring agent consisting of a single coloring agent. is preferably a combination of chromatic colorants.

The black composition is preferably a combination of two or more organic pigments selected from, for example, five organic pigments of blue, purple, yellow, red, and orange.
By combining two or more organic pigments out of the above five organic pigments, a pseudo-blackened hue can be expressed. Here, "pseudo-black" is ideally chromatically black, but any hue that is acceptable in the application of a black film formed using a black composition is acceptable.

The ratio (mass ratio) of the organic pigments of each hue in the black composition exhibiting pseudo black is preferably (blue organic pigment) / (yellow organic pigment + orange organic pigment) / (red organic pigment + purple organic pigment) = (30% by mass or more and 60% by mass or less)/(0% by mass or more and 50% by mass or less)/(5% by mass or more and 70% by mass or less).

As the above five organic pigments, conventionally known ones can be used.
As a blue organic pigment, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, and C.I. I. Pigment Blue 60 may be mentioned.
As a purple organic pigment, C.I. I. Pigment Violet 19, and C.I. I. Pigment Violet 23 may be mentioned.
As a yellow organic pigment, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180, and C.I. I. Pigment Yellow 181 may be mentioned.
As an orange organic pigment, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 69, C.I. I. Pigment Orange 71, and C.I. I. Pigment Orange 73 may be mentioned.
As a red organic pigment, C.I. I. Pigment Red 122, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179, C.I. I. Pigment Red 242, C.I. I. Pigment Red 224, C.I. I. Pigment Red 254, C.I. I. Pigment Red 256, C.I. I. Pigment Red 264, and C.I. I. Pigment Red 272 may be mentioned.

Among them, the blue organic pigment is C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 15:6 is at least one selected from the group consisting of C.I. I. Pigment Violet 23 and the yellow organic pigment is C.I. I. Pigment Yellow 83 and/or C.I. I. Pigment Yellow 139, and the orange organic pigment is C.I. I. Pigment Orange 43 and/or C.I. I. Pigment Orange 64 and the red organic pigment is C.I. I. Pigment Red 254 and/or C.I. I. Pigment Red 256, is preferred.
By using these organic pigments in combination, it is easy to form a black cured film having a good black hue and excellent optical density (OD value).
be.

In order to obtain a pseudo-black black composition, it is preferable to combine at least one selected from a blue organic pigment, a yellow organic pigment, and an orange organic pigment, and these organic pigments and a red organic pigment are combined. and at least one organic pigment selected from violet organic pigments.
Specific combinations of pigments belonging to organic pigments of each color include, for example,
・C. I. Pigment Blue 15:4 and C.I. I. Pigment Yellow 139 and C.I. I. Combination with Pigment Red 254,
・C. I. Pigment Blue 15:6 and C.I. I. Pigment Orange 64 and C.I. I. combination with Pigment Violet 23,
・C. I. Pigment Blue 15:4 or 15:3 and C.I. I. Pigment Yellow 83 and C.I. I. Pigment Violet 23 and C.I. I. in combination with Pigment Red 254, and
・C. I. Pigment Blue 15:6 and C.I. I. Pigment Violet 23 and C.I. I. A combination with Pigment Red 256 is preferred.

A dispersant may be further used to uniformly disperse the coloring agent (E) in the photosensitive resin composition. 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 colorant (E), it is preferable to use an acrylic resin-based dispersant as the dispersant.
In some cases, corrosive gas originating from the dispersant is generated from the cured film. Therefore, it is also a preferred embodiment that the pigment is dispersed without using a dispersant.

In addition, in the photosensitive resin composition, a pigment and a dye may be used in combination. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the photosensitive 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 mentioned.
Further, these dyes can be dispersed in an organic solvent or the like by forming a lake (chlorination) and used as the colorant (E).
In addition to these dyes, for example, JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. The described dyes and the like can also be preferably used.

The amount of the coloring agent (E) used in the photosensitive resin composition can be appropriately selected within a range that does not hinder the object of the present invention. Typically, the amount of the coloring agent (E) used is preferably 2% by mass or more and 75% by mass or less, and 3% by mass or more and 70% by mass or less, based on the total mass of the solid content of the photosensitive resin composition. more preferred.

In particular, when forming a black matrix using a photosensitive resin composition, the amount of the light-shielding agent (E1) in the photosensitive resin composition is adjusted so that the OD value per 1 μm of the black matrix film is 4 or more. Adjusting is preferred. If the OD value per 1 μm of film in the black matrix is 4 or more, sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display.

When a pigment is used as the colorant (E), it is preferable that the pigment is dispersed in the presence or absence of a dispersant at an appropriate concentration and then added to the photosensitive resin composition after forming a dispersion liquid.
In this specification, the amount of the pigment used can be defined as a value including the present dispersant.

<Imidazole generator (F)>
The photosensitive resin composition may contain an imidazole generator (F) that generates an imidazole compound represented by the following formula (F1) upon exposure. When the photosensitive resin composition contains such an imidazole generator (F), the photosensitive resin composition is easily cured by exposure, and a patterned cured film having a good cross-sectional shape is easily formed. .

式（Ｆ１）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基である。

In formula (F1), R ^f1 , R ^f2 , and R ^f3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino groups, phosphinyl groups, phosphonate groups, or organic groups.

In the imidazole compound represented by formula (F1), examples of the organic group for R ^f1 , R ^f2 , and R ^f3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like. be done. The organic group may contain a bond or substituent other than the hydrocarbon group, such as a heteroatom. Moreover, the organic group may be linear, branched, or cyclic. The organic group is usually monovalent, but can be a divalent or higher organic group when forming a cyclic structure.

R ^f1 and R ^f2 may combine to form a cyclic structure, and may further contain a heteroatom bond. The cyclic structure includes a heterocycloalkyl group, a heteroaryl group, and the like, and may be a condensed ring.

The bonds contained in the organic groups of R ^f1 , R ^f2 , and R ^f3 are not particularly limited as long as the effects of the present invention are not impaired, and the organic groups contain heteroatoms such as oxygen atoms, nitrogen atoms, and silicon atoms. May contain a bond. Specific examples of bonds containing heteroatoms include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N=C(-R)-, -C(= NR)-: R represents a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, sulfinyl bond and azo bond.

When the organic groups as R ^f1 , R ^f2 and R ^f3 are substituents other than hydrocarbon groups, R ^f1 , R ^f2 and R ^f3 are not particularly limited as long as the effects of the present invention are not impaired. Specific examples of R ^f1 , R ^f2 and R ^f3 include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, alkyl ether group, alkenyl Examples include ether groups, alkylthioether groups, alkenylthioether groups, arylether groups, and arylthioether groups. A hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

R ^f1 , R ^f2 , and R ^f3 are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen Atoms are preferred, and hydrogen atoms are more preferred.

The imidazole generator (F) is not particularly limited as long as it is a compound capable of generating an imidazole compound represented by formula (F1) upon exposure.
As the imidazole generator (F), for example, in a well-known photosensitive amine generator, a group derived from an amine generated by the amine generator is substituted with a group derived from an imidazole compound represented by the formula (F1). can be used.

From the viewpoint of compatibility with the components contained in the photosensitive resin composition, suitable imidazole generators (F) include compounds represented by the following formula (F1-1).

式（Ｆ１－１）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。
Ｒ^ｆ１１及びＲ^ｆ１２は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基である。Ｒ^ｆ１３、Ｒ^ｆ１４、Ｒ^ｆ１５、Ｒ^ｆ１６、及びＲ^ｆ１７は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。Ｒ^ｆ１３、Ｒ^ｆ１４、Ｒ^ｆ１５、Ｒ^ｆ１６、及びＲ^ｆ１７は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。
で表される化合物が挙げられる。

In formula (F1-1), R ^f1 , R ^f2 and R ^f3 are the same as in formula (F1).
R ^f11 and R ^f12 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, and a phosphinyl group. , a phosphono group, a phosphonato group, or an organic group. R ^f13 , R ^f14 , R ^f15 , R ^f16 and R ^f17 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group. Two or more of R ^f13 , R ^f14 , R ^f15 , R ^f16 and R ^f17 may combine to form a cyclic structure, and may contain a heteroatom bond.
The compound represented by is mentioned.

Examples of the organic group for R ^f11 and R ^f12 include the organic groups exemplified for R ^f1 , R ^f2 and R ^f3 in formula (F1). The organic group as R ^f11 and R ^f12 may contain a heteroatom in the organic group as in the case of R ^f1 , R ^f2 and R ^f3 . Moreover, the organic group may be linear, branched, or cyclic.

Among the above, R ^f11 and R ^f12 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and a cycloalkyl group having 4 to 13 carbon atoms. alkenyl group, aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having cyano group, and 1 or more carbon atoms having hydroxyl group an alkyl group having 10 or less carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, substituted with an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group), an aryl group having 6 to 20 carbon atoms, an electron-donating group and/or an electron-withdrawing group An aryl group having 6 to 20 carbon atoms, a benzyl group, a cyano group and a methylthio group substituted with an electron donating group and/or an electron withdrawing group are preferred. More preferably, both R ^f11 and R ^f12 are hydrogen atoms, or R ^f11 is a methyl group and R ^f12 is a hydrogen atom.

In formula (F1-1), R ^f13 , R ^f14 , R ^f15 , R ^f16 and R ^f17 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group and a nitro group. , a nitroso group, a sulphino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group.

Examples of organic groups for R ^f13 , R ^f14 , R ^f15 , R ^f16 and R ^f17 include the organic groups exemplified for R ^f1 , R ^f2 and R ^f3 in formula (F1). The organic groups as R ^f13 , R ^f14 , R ^f15 , R ^f16 and R ^f17 may contain heteroatoms in the organic groups, as in the case of R ^f1 , R ^f2 and R ^f3 . Moreover, the organic group may be linear, branched, or cyclic.

Two or more of R ^f13 , R ^f14 , R ^f15 , R ^f16 and R ^f17 may combine to form a cyclic structure, and may contain a heteroatom bond. The cyclic structure includes a heterocycloalkyl group, a heteroaryl group, and the like, and may be a condensed ring. For example, R ^f13 , R ^f14 , R ^f15 , R ^f16 , and R ^f17 are benzene to which two or more of them are attached to which R ^f13 , R ^f14 , R ^f15 , R ^f16 , and R ^f17 are attached. Ring atoms may be shared to form fused rings such as naphthalene, anthracene, phenanthrene, and indene.

Among the above, R ^f13 , R ^f14 , R ^f15 , R ^f16 , and R ^f17 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 13 carbon atoms. , a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an alkyl having 2 to 11 carbon atoms having a cyano group an alkyl group having 1 to 10 carbon atoms and a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, carbon an acyl group having 1 to 10 atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an electron donating group and/or an electron withdrawing group substituted with 6 carbon atoms A benzyl group, a cyano group, a methylthio group and a nitro group substituted with 20 or less aryl groups, electron-donating groups and/or electron-withdrawing groups are preferred.

R ^f13 , R ^f14 , R ^f15 , R ^f16 , and R ^f17 are two or more of them bonded together to form R ^f13 , R ^f14 , R ^f15 , R ^f16 , and R ^f17 A condensed ring such as naphthalene, anthracene, phenanthrene, or indene is also preferably formed by sharing the atoms of the benzene ring.

Among the compounds represented by the above formula (F1-1), compounds represented by the following formula (F1-2) are preferred.

式（Ｆ１－２）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。Ｒ^ｆ１１～Ｒ^ｆ１６は式（Ｆ１－１）と同様である。Ｒ^ｆ１８は、水素原子又は有機基を示す。式（Ｆ１－２）において、Ｒ^ｆ１３及びＲ^ｆ１４が水酸基となることはない。Ｒ^ｆ１３、Ｒ^ｆ１４、Ｒ^ｆ１５、及びＲ^ｆ１６は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。

In formula (F1-2), R ^f1 , R ^f2 and R ^f3 are the same as in formula (F1). R ^f11 to R ^f16 are the same as in formula (F1-1). R ^f18 represents a hydrogen atom or an organic group. In formula (F1-2), R ^f13 and R ^f14 are never hydroxyl groups. Two or more of R ^f13 , R ^f14 , R ^f15 and R ^f16 may combine to form a cyclic structure and may contain a heteroatom bond.

Since the compound represented by formula (F1-2) has the substituent ^{—OR f18} , it has particularly excellent affinity with each component contained in the photosensitive resin composition.

In formula (F1-2), R ^f18 is a hydrogen atom or an organic group. When R ^f18 is an organic group, examples of the organic group include the organic groups exemplified for R ^f1 , R ^f2 and R ^f3 in formula (F1). The organic group may contain a heteroatom within the organic group. Moreover, the organic group may be linear, branched, or cyclic. R ^f18 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group.

Specific examples of compounds particularly suitable as the compound represented by Formula (F1-1) are shown below.

A compound represented by the following formula (F1-2) is also preferred as the imidazole generator (F).

式（Ｆ１－２）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。Ｒ^ｆ２１は、水素原子、又は１価の有機基である。Ｒ^ｆ２２は置換基を有してもよい芳香族基である。Ｒ^ｆ２１は他方のＲ^ｆ２１又はＲ^ｆ２２と結合して環状構造を形成してもよい。

In formula (F1-2), R ^f1 , R ^f2 and R ^f3 are the same as in formula (F1). R ^f21 is a hydrogen atom or a monovalent organic group. R ^f22 is an aromatic group optionally having a substituent. R ^f21 may combine with the other R ^f21 or R ^f22 to form a cyclic structure.

In formula (F1-2), R ^f21 is a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and may be, for example, an optionally substituted alkyl group, an optionally substituted aromatic group, or the like. When R ^f21 is an alkyl group, the alkyl group may have an ester bond or the like in the chain.

The alkyl group may be, for example, the same as R ^f24 in formula (F1-2-1) described later. The number of carbon atoms in the alkyl group is preferably 1 or more and 40 or less, more preferably 1 or more and 30 or less, particularly preferably 1 or more and 20 or less, and most preferably 1 or more and 10 or less.
The substituent that the alkyl group may have may be, for example, the same as the substituent that the alkylene group represented by R ^f25 in formula (F1-2-1) described later may have.

The aromatic group which may have a substituent is the same as R f22 in formula ( ^F1-2-1 ) described later, preferably an aryl group, more preferably a phenyl group. The optionally substituted aromatic group as R ^f21 may be the same as or different from R ^f22 .
In formula (F1-2), one R ^f21 is preferably a hydrogen atom, one R ^f21 is a hydrogen atom and the other R ^f21 is an optionally substituted alkyl group or a substituent It is more preferably an aromatic group that may be
In formula (F1-2), R ^f21 may combine with the other R ^f21 or R ^f22 to form a cyclic structure. For example, when at least one R ^f21 is an optionally substituted alkyl group, R ^f21 may combine with the other R ^f21 or R ^f22 to form a cyclic structure.

The compound represented by formula (F1-2) may be a compound represented by formula (F1-2-1) below.

式（Ｆ１－２－１）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。Ｒ^ｆ２３は水素原子又はアルキル基である。Ｒ^ｆ２２は置換基を有してもよい芳香族基である。Ｒ^ｆ２４は置換基を有してもよいアルキレン基である。Ｒ^ｆ２４はＲ^ｆ２２と結合して環状構造を形成してもよい。

In formula (F1-2-1), R ^f1 , R ^f2 and R ^f3 are the same as in formula (F1). R ^f23 is a hydrogen atom or an alkyl group. R ^f22 is an aromatic group optionally having a substituent. R ^f24 is an optionally substituted alkylene group. R ^f24 may combine with R ^f22 to form a cyclic structure.

In formula (F1-2-1), R ^f23 is a hydrogen atom or an alkyl group. When R ^f23 is an alkyl group, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

Specific examples of alkyl groups suitable for R ^f23 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups.

In formula (F1-2-1), R ^f22 is an optionally substituted aromatic group. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

The type of aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, and may be formed by condensation of two or more aromatic hydrocarbon groups. may be formed by combining with a single bond. Preferred aromatic hydrocarbon groups are phenyl, naphthyl, biphenylyl, anthryl and phenanthrenyl groups.

The type of aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Preferred aromatic heterocyclic groups are pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl, and benzimidazolyl groups.

Substituents that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, and nitroso groups. , sulfino groups, sulfo groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonato groups, amino groups, ammonio groups, and organic groups. When the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group has multiple substituents, the multiple substituents may be the same or different.

When the substituent of the aromatic group is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. Moreover, this organic group may be linear, branched, cyclic, or a combination of these structures. This organic group is usually monovalent, but may be a divalent or higher organic group when forming a cyclic structure.

When an aromatic group has substituents on adjacent carbon atoms, two substituents attached on adjacent carbon atoms may be joined together to form a cyclic structure. Cyclic structures include aliphatic hydrocarbon rings and heteroatom-containing aliphatic rings.

When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effects of the present invention are not impaired, and the organic group may be an oxygen atom, a nitrogen atom, a silicon atom, or the like. may contain a bond containing a heteroatom of Specific examples of bonds containing heteroatoms include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N=C(-R)-, -C(= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

When the organic group is a substituent other than a hydrocarbon group, the type of the substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of substituents other than hydrocarbon groups include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, and alkoxy groups. , alkoxycarbonyl group, amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, alkyl ether group, alkenyl ether group, alkylthioether group, alkenylthioether group, arylether group, arylthioether group and the like. A hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Substituents possessed by a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group include an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 carbon atom. An alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom are preferable.

As R ^f22 , an imidazole compound represented by formula (F1-2) or formula (F1-2-1) can be synthesized inexpensively and easily, and the imidazole compound has good solubility in water and organic solvents. , a phenyl group, a furyl group, and a thienyl group, each of which may have a substituent.

In formula (F1-2-1), R ^f24 is an optionally substituted alkylene group. The substituents that the alkylene group may have are not particularly limited as long as the objects of the present invention are not impaired. Specific examples of the substituent that the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom, and the like. The alkylene group may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is not particularly limited, and is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less. The number of carbon atoms in the alkylene group does not include the carbon atoms of the substituents bonded to the alkylene group.

An alkoxy group as a substituent bonded to an alkylene group may be a straight-chain alkoxy group or a branched-chain alkoxy group. The number of carbon atoms in the alkoxy group as a substituent is not particularly limited, and is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

An amino group as a substituent bonded to an alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or dialkylamino group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms in the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, and is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

Specific examples of alkylene groups suitable for R ^f24 include methylene, ethane-1,2-diyl, n-propane-1,3-diyl, n-propane-2,2-diyl, and n-butane. -1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl group group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group , n-octadecane-1,18-diyl group, n-nonadecane-1,19-diyl group, and n-icosane-1,20-diyl group.

Among the imidazole compounds represented by the above formula (F1-2), compounds represented by the following formula (F1-2-2) are preferred because they can be synthesized inexpensively and easily.

式（Ｆ１－２－２）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。Ｒ^ｆ２１は、式（Ｆ１－２）と同じであり、Ｒ^ｆ２５、Ｒ^ｆ２６、Ｒ^ｆ２７、Ｒ^ｆ２８、及びＲ^ｆ２９は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^ｆ２５、Ｒ^ｆ２６、Ｒ^ｆ２７、Ｒ^ｆ２８、及びＲ^ｆ２９のうち少なくとも１つは水素原子以外の基である。Ｒ^ｆ２５、Ｒ^ｆ２６、Ｒ^ｆ２７、Ｒ^ｆ２８、及びＲ^ｆ２９のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^ｆ２１はＲ^ｆ２７と結合して環状構造を形成してもよい。

In formula (F1-2-2), R ^f1 , R ^f2 and R ^f3 are the same as in formula (F1). R ^f21 is the same as in Formula (F1-2), and R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group. However, at least one of R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 is a group other than a hydrogen atom. At least two of R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 may combine to form a cyclic structure. R f21 may ^{combine with R f27 to} form a cyclic structure.

R ^f25 , R ^f26 , R ^f27 , R ^f28 , and R ^f29 are the same as in formula (F1-2-3) described later. In formula (F1-2-2), R ^f21 may combine with R ^f27 to form a cyclic structure. For example, when R ^f21 is an optionally substituted alkyl group, R f21 may ^{combine with R f27 to} form a cyclic structure.

Among the imidazole compounds represented by the above formula (F1-2-1) or (F1-2-2), the following compounds can be synthesized inexpensively and easily, and have excellent solubility in water and organic solvents. A compound represented by the formula (F1-2-3) is preferred, and a compound represented by the formula (F1-2-3) in which R ^f24 is a methylene group is more preferred.

式（Ｆ１－２－３）中、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。Ｒ^ｆ２３、及びＲ^ｆ２４は、式（Ｆ１－２－１）と同様である。Ｒ^ｆ２５、Ｒ^ｆ２６、Ｒ^ｆ２７、Ｒ^ｆ２８、及びＲ^ｆ２９は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^ｆ２５、Ｒ^ｆ２６、Ｒ^ｆ２７、Ｒ^ｆ２８、及びＲ^ｆ２９のうち少なくとも１つは水素原子以外の基である。Ｒ^ｆ２５、Ｒ^ｆ２６、Ｒ^ｆ２７、Ｒ^ｆ２８、及びＲ^ｆ２９のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^ｆ２４はＲ^ｆ２７と結合して環状構造を形成してもよい。

In formula (F1-2-3), R ^f1 , R ^f2 and R ^f3 are the same as in formula (F1). R ^f23 and R ^f24 are the same as in formula (F1-2-1). R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group. However, at least one of R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 is a group other than a hydrogen atom. At least two of R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 may combine to form a cyclic structure. R ^f24 may combine with R ^f27 to form a cyclic structure.

When R ^f25 , R ^f26 , R ^f27 , R ^f28 , and R ^f29 are organic groups, the organic groups are the same as the organic groups that R f22 in formula ( ^F1-2-1 ) has as a substituent. R ^f25 , R ^f26 , R ^f27 and R ^f28 are preferably hydrogen atoms.

Among them, at least one of R ^f25 , R ^f26 , R ^f27 , R ^f28 and R ^f29 is preferably the following substituent, and R ^f29 is particularly preferably the following substituent. When R ^f29 is the following substituent, R ^f25 , R ^f26 , R ^f27 and R ^f28 are preferably hydrogen atoms.
^{-OR f30}
(R ^f30 is a hydrogen atom or an organic group.)

When R ^f30 is an organic group, the organic group is the same as the organic group that R f22 in formula ( ^F1-2-1 ) has as a substituent. R ^f30 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

式（Ｆ１－２－４）において、Ｒ^ｆ１、Ｒ^ｆ２、及びＲ^ｆ３は、式（Ｆ１）と同様である。Ｒ^ｆ２３は、式（Ｆ１－２－１）と同様である。Ｒ^ｆ３１、Ｒ^ｆ３２、Ｒ^ｆ３３、Ｒ^ｆ３４、及びＲ^ｆ３５は、それぞれ独立に、水素原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^ｆ３１、Ｒ^ｆ３２、Ｒ^ｆ３３、Ｒ^ｆ３４、及びＲ^ｆ３５のうち少なくとも１つは水素原子以外の基である。 Among the compounds represented by the above formula (F1-2-3), compounds represented by the following formula (F1-2-4) are preferred.

In formula (F1-2-4), R ^f1 , R ^f2 , and R ^f3 are the same as in formula (F1). R ^f23 is the same as in formula (F1-2-1). R ^f31 , R ^f32 , R ^f33 , R ^f34 and R ^f35 each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group. However, at least one of R ^f31 , R ^f32 , R ^f33 , R ^f34 and R ^f35 is a group other than a hydrogen atom.

Among the compounds represented by formula (F1-2-4), at least one of R ^f31 , R ^f32 , R ^f33 , R ^f34 and R ^f35 is a group represented by ^{—OR f30} described above. is preferred, and it is particularly preferred that R ^f35 is a group represented by ^{—OR f30} . When R ^f35 is a group represented by ^—OR f30, R ^f32 , R ^f33 , R ^f34 and R ^f35 are preferably hydrogen atoms.

Suitable specific examples of the imidazole compound represented by formula (F1-2) or formula (F1-2-1) include the following compounds.

The content of the imidazole generator (F) in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of the imidazole generator (F) is typically 0.01 parts by mass or more and 2.5 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the photopolymerizable monomer (B). Part by mass is preferred, and 0.01 to 0.5 part by mass is more preferred. When the content of the imidazole generator (F) in the photosensitive resin composition is within such a range, it is easy to form a patterned cured film with a favorable cross-sectional shape.

<Sensitizer (G)>
The photosensitive resin composition may contain a sensitizer (G) together with the above photopolymerization initiator. Since the photosensitive resin composition contains the sensitizer (G), it can be cured satisfactorily even when using a light source with low irradiation energy such as LED exposure.

As the sensitizer (G), any compound conventionally used for the purpose of sensitizing a photopolymerization initiator in a photosensitive resin composition can be used without particular limitation.

The sensitizer (G) is preferably a compound having at least one substituent selected from the group consisting of an alkoxy group, a substituted carbonyloxy group and an oxo group (=O). As the compound having the substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferable.
The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O). Examples of substituents include alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, alkoxyalkyl groups having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. , an aromatic acyl group having 7 to 11 carbon atoms (aroyl group), a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, a mercapto group, and the like.

Alkoxy groups can be straight or branched. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 12, and particularly preferably from 1 to 6.
Suitable examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n -heptyloxy group, n-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, n-decyloxy group and the like.

A substituted carbonyloxy group is a group represented by —O—CO—A ^g . Ag is not particularly limited as long as the sensitizer ( ^G ) has the desired sensitizing action, and may be various organic groups. A is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. .

An aryl group or an aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as it does not interfere with the object of the present invention. When the aryl group or aryloxy group has multiple substituents, the multiple substituents may be the same or different.
Preferred examples of substituents include alkoxy groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and 6 to 10 carbon atoms. an aryloxy group, an aliphatic acyl group having 2 to 7 carbon atoms, an aromatic acyl group having 7 to 11 carbon atoms (aroyl group), a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and A mercapto group and the like can be mentioned.

When ^Ag is an alkyl group or an alkoxy group, these groups may be linear or branched.
Preferable examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. , n-octyl group, and 2-ethylhexyl group.
Preferable examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl and β-naphthyl groups.
Suitable examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy and n-hexyloxy groups. , n-heptyloxy group, n-octyloxy group, and 2-ethylhexyloxy group.

In a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound substituted with one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O) , The number of rings constituting the condensed ring is not particularly limited as long as the desired sensitizing effect is obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 or more and 6 or less, and most preferably 3 or 4.
As long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the single ring forming the condensed polycyclic ring may not necessarily be an aromatic ring.

Preferable examples of the condensed polycyclic ring contained in the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound include acenaphthylene ring, phenanthrene ring, anthracene ring, naphthacene ring, xanthene ring, and thio A xanthene ring is mentioned. Among these rings, anthracene ring, naphthacene ring and thioxanthene ring are preferred.

Specific examples of compounds containing an anthracene ring and suitable for use as the sensitizer (G) include 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9 , 10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutylcarbonyloxy)anthracene , 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(n-heptylcarbonyloxy)anthracene, 9,10-bis(2 -ethylhexanoyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10-bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n-decylcarbonyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(2-naphthoyloxy)anthracene, 2-methyl-9,10-bis(acetyl oxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isopropylcarbonyloxy) ) anthracene, 2-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentyl carbonyloxy)anthracene, 2-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-methyl-9,10-bis(benzoyloxy)anthracene, 2-methyl-9,10-bis(4- methylbenzoyloxy)anthracene, 2-methyl-9,10-bis(2-naphthoyloxy)anthracene, 1-methyl-9,10-bis(acetyloxy)anthracene, 1-methyl-9,10-bis(propionyl) oxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isopropylcarbonyloxy)anthracene n, 1-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-pentylcarbonyl oxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9,10-bis(benzoyloxy)anthracene, 1-methyl-9,10-bis(4-methyl benzoyloxy)anthracene, 1-methyl-9,10-bis(2-naphthoyloxy)anthracene, 2-ethyl-9,10-bis(acetyloxy)anthracene, 2-ethyl-9,10-bis(propionyloxy) ) anthracene, 2-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-butyl carbonyloxy)anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n -hexylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(benzoyloxy)anthracene, 2-ethyl-9,10-bis(4-ethyl-benzoyloxy)anthracene, 2-ethyl-9,10-bis (2-naphthoyloxy)anthracene, 1-ethyl-9,10-bis(acetyloxy)anthracene, 1-ethyl-9,10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n -propylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isopropylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-ethyl-9,10-bis (isobutylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-ethyl-9,10 -bis(benzoyloxy)anthracene, 1-ethyl-9,10-bis(4-ethyl-benzoyloxy)anthracene, 1-ethyl-9,10-bis(2-naphthoyloxy)anthracene, 1-(tert- butyl)-9,1 0-bis(n-propylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-butylcarbonyl oxy)anthracene, 1-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-(tert -butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 1-(t-butyl)-9,10-bis (4-(tert-butyl)-benzoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-(tert-butyl)-9,10-bis( n-propylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(tert-butyl)- 9,10-bis(n-hexylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(4-( t-butyl)-benzoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-pentyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(benzoyloxy)anthracene , 2-pentyl- 9,10-bis(4-(tert-butyl)-benzoyloxy)anthracene, 2-pentyl-9,10-bis(2-naphthoyloxy)anthracene and the like.

Halogen-substituted anthracene compounds are also preferred as sensitizers (G). A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Specific examples of halogen-substituted anthracene compounds preferred as the sensitizer (G) include 2-chloro-9,10-bis(acetyloxy)anthracene, 2-chloro-9,10- Bis(propionyloxy)anthracene, 2-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-chloro-9,10-bis (n-butylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-chloro-9,10 -bis(n-hexylcarbonyloxy)anthracene, 2-chloro-9,10-bis(benzoyloxy)anthracene, 2-chloro-9,10-bis(4-methylbenzoyloxy)anthracene, 2-chloro-9, 10-bis(2-naphthoyloxy)anthracene, 1-chloro-9,10-bis(acetyloxy)anthracene, 1-chloro-9,10-bis(propionyloxy)anthracene, 1-chloro-9,10- bis(n-propylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-chloro-9, 10-bis(isobutylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-chloro- 9,10-bis(benzoyloxy)anthracene, 1-chloro-9,10-bis(4-methylbenzoyloxy)anthracene, 1-chloro-9,10-bis(2-naphthoyloxy)anthracene, 2-fluoro -9,10-bis(acetyloxy)anthracene, 2-fluoro-9,10-bis(propionyloxy)anthracene, 2-fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-fluoro-9 , 10-bis(isopropylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(isobutylcarbonyloxy)anthracene , 2-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(benzoyloxy) Anthracene, 2-fluoro-9,10-bis(4-methylbenzoyloxy)anthracene, 2-fluoro-9,10-bis(2-naphthoyloxy)anthracene, 1-fluoro-9,10-bis(acetyloxy) ) anthracene, 1-fluoro-9,10-bis(propionyloxy)anthracene, 1-fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isopropylcarbonyloxy) Anthracene, 1-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isobutylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-pentylcarbonyl) oxy)anthracene, 1-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(benzoyloxy)anthracene, 1-fluoro-9,10-bis(4-methyl benzoyloxy)anthracene, 1-fluoro-9,10-bis(2-naphthoyloxy)anthracene, 2-bromo-9,10-bis(acetyloxy)anthracene, 2-bromo-9,10-bis(propionyloxy) ) anthracene, 2-bromo-9,10-bis(n-propylcarbonyloxy)anthracene, 2-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-butyl carbonyloxy)anthracene, 2-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n -hexylcarbonyloxy)anthracene, 2-bromo-9,10-bis(benzoyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzoyloxy)anthracene, 2-bromo-9,10-bis( 2-naphthoyloxy)anthracene, 1-bromo-9,10-bis(acetyloxy)anthracene, 1-bromo-9,10-bis(propionyloxy)anthracene, 1-bromo-9,10-bi Su(n-propylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-butylcarbonyloxy)anthracene, 1-bromo-9, 10-bis(isobutylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-bromo- 9,10-bis(benzoyloxy)anthracene, 1-bromo-9,10-bis(4-methylbenzoyloxy)anthracene, 1-bromo-9,10-bis(2-naphthoyloxy)anthracene and the like. be done.

Anthracene compounds substituted with alkoxy groups are also preferred as sensitizers (G).
Specific examples of an anthracene compound substituted with an alkoxy group and preferred as the sensitizer (G) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis(n- Propyloxy)anthracene, 9,10-bis(n-butyloxy)anthracene, 9,10-bis(n-pentyloxy)anthracene, 9,10-bis(isopentyloxyoxy)anthracene, 9,10-bis(n -hexyloxy)anthracene, 9,10-bis(n-heptyloxy)anthracene, 9,10-bis(n-octyloxy)anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-(n-propyloxy)anthracene, 9-(n-butyloxy)anthracene, 9-(n-pentyloxy)anthracene, 9-(isopentyloxyoxy)anthracene, 9-(n-hexyl) oxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy)anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9 , 10-diethoxyanthracene, 2-methyl-9,10-bis(n-propyloxy)anthracene, 2-methyl-9,10-bis(n-butyloxy)anthracene, 2-methyl-9,10-bis( n-pentyloxy)anthracene, 2-methyl-9,10-bis(isopentyloxy)anthracene, 2-methyl-9,10-bis(n-hexyloxy)anthracene, 2-methyl-9,10-bis (n-heptyloxy)anthracene, 2-methyl-9,10-bis(n-octyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-ethyl-9,10- Dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-bis(n-propyloxy)anthracene, 2-ethyl-9,10-bis(n-butyloxy)anthracene, 2- ethyl-9,10-bis(n-pentyloxy)anthracene, 2-ethyl-9,10-bis(isopentyloxy)anthracene, 2-ethyl-9,10-bis(n-hexyloxy)anthracene, 2 -ethyl-9,10-bis(n- butyloxy)anthracene, 2-ethyl-9,10-bis(n-octyloxy)anthracene, 2-ethyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-methyl-9-methoxyanthracene, 2-methyl -9-ethoxyanthracene, 2-methyl-9-(n-propyloxy)anthracene, 2-methyl-9-(n-butyloxy)anthracene, 2-methyl-9-(n-pentyloxy)anthracene, 2-methyl -9-(isopentyloxy)anthracene, 2-methyl-9-(n-hexyloxy)anthracene, 2-methyl-9-(n-heptyloxy)anthracene, 2-methyl-9-(n-octyloxy) ) anthracene, 2-methyl-9-(2-ethylhexyloxy)anthracene, 2-ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9-(n-propyloxy)anthracene, 2 -ethyl-9-(n-butyloxy)anthracene, 2-ethyl-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxy)anthracene, 2-ethyl-9-(n-hexyl) oxy)anthracene, 2-ethyl-9-(n-heptyloxy)anthracene, 2-ethyl-9-(n-octyloxy)anthracene, 2-ethyl-9-(2-ethylhexyloxy)anthracene, 2-chloro- 9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis(n-propyloxy)anthracene, 2-chloro-9,10-bis(n-butyloxy) Anthracene, 2-chloro-9,10-bis(n-pentyloxy)anthracene, 2-chloro-9,10-bis(isopentyloxy)anthracene, 2-chloro-9,10-bis(n-hexyloxy) ) anthracene, 2-chloro-9,10-bis(n-heptyloxy)anthracene, 2-chloro-9,10-bis(n-octyloxy)anthracene, 2-chloro-9,10-bis(2-ethylhexyl oxy)anthracene, 2-bromo-9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo-9,10-bis(n-propyloxy)anthracene, 2-bromo-9, 10-bis(n-butyloxy)anthracene, 2-bromo-9,10-bis (n-pentyloxy)anthracene, 2-bromo-9,10-bis(isopentyloxy)anthracene, 2-bromo-9,10-bis(n-hexyloxy)anthracene, 2-bromo-9,10- Bis(n-heptyloxy)anthracene, 2-bromo-9,10-bis(n-octyloxy)anthracene, 2-bromo-9,10-bis(2-ethylhexyloxy)anthracene, 2-chloro-9-methoxy anthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9-(n-propyloxy)anthracene, 2-chloro-9-(n-butyloxy)anthracene, 2-chloro-9-(n-pentyloxy) Anthracene, 2-chloro-9-(isopentyloxy)anthracene, 2-chloro-9-(n-hexyloxy)anthracene, 2-chloro-9-(n-heptyloxy)anthracene, 2-chloro-9- (n-octyloxy)anthracene, 2-chloro-9-(2-ethylhexyloxy)anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9-(n-propyl oxy)anthracene, 2-bromo-9-(n-butyloxy)anthracene, 2-bromo-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxyoxy)anthracene, 2-bromo-9 -(n-hexyloxy)anthracene, 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, and 2-bromo-9-(2-ethylhexyloxy) anthracene and the like.

Among the anthracene compounds described above, 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9 , 10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutylcarbonyloxy)anthracene , 9,10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis(2 -ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene are preferred.

Specific examples of the compound containing a naphthacene ring and suitably used as the sensitizer (G) include:
2-methyl-5,11-dioxo-6,12-bis(acetyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(propionyloxy)naphthacene, 2-methyl-5,11- dioxo-6,12-bis(n-propylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6, 12-bis(n-butylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis( n-pentylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n- heptylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(acetyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(propionyloxy)naphthacene, 2- ethyl-5,11-dioxo-6,12-bis(n-propylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(n-butylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis(n-pentylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6 , 12-bis(n-heptylbornyloxy) naphthacene compounds substituted with alkylcarbonyloxy groups such as naphthacene;
2-methyl-5,11-dioxo-6,12-bis(benzoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2-methyl-5 , 11-dioxo-6,12-bis(m-toluoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene, 2-methyl-5,11 -dioxo-6,12-bis(α-naphthoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene, 2-ethyl-5,11-dioxo -6,12-bis(benzoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12- bis(m-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis( aroyloxy group-substituted naphthacene compounds such as α-naphthoyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene;
2-methyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-methyl-5, 11-dioxo-6,12-bis(n-propyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 2-methyl-5,11- Dioxo-6,12-bis(n-butyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-pentyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-heptyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis(methoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis( n-propyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n- Butyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-pentyloxy carbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-heptyloxy alkoxycarbonyloxy group-substituted naphthacene compounds such as carbonyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene;
2-methyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-methyl -5,11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-methyl -5,11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene, 2-ethyl -5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5, Aroyloxycarbonyls such as 11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene Oxy group-substituted naphthacene compounds can be mentioned.

Among the above naphthacene ring-containing compounds, 5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 5,11- Dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(n-butylcarbonyl) oxy)naphthacene, 5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)naphthacene and 5,11-dioxo-6,12-bis(n-heptanoyloxy)naphthacene are preferred.

Specific examples of compounds containing a thioxanthene ring suitably used as the sensitizer (G) include thioxanthene-9-one, 2-methyl-9H-thioxanthene-9-one, 2-isopropyl-9H- thioxanthen-9-one, 1,4-dimethylthioxanthen-9-one, 3-methyl-9-oxo-9H-thioxanthen-2-yl acetate and the like.

The content of the sensitizer (G) is preferably 5 parts by mass or more and 60 parts by mass or less, and 15 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the photopolymerization initiator (C) in the photosensitive resin composition. is more preferred. When the photosensitive resin composition contains the sensitizer within the above range, the curing reaction by exposure proceeds uniformly, and it is easy to form a patterned cured film with particularly good edge angles.

<Organic solvent (S)>
The photosensitive resin composition may typically contain an organic solvent (S) for the purpose of adjusting coatability. Examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and 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 (poly ) Alkylene glycol monoalkyl ethers; (poly)alkylenes such as 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, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, Lactic acid alkyl esters such as ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid ethyl, 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, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N,N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent (S) used can be appropriately determined according to the application of the photosensitive resin composition. An example of the amount of the organic solvent (S) to be used is an amount in which the solid content concentration of the photosensitive resin composition is in the range of 1% by mass or more and 50% by mass or less.

<Other ingredients>
If necessary, the photosensitive resin composition may contain other various additives. Specific examples include dispersing aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like.

Thermal polymerization inhibitors used in the photosensitive resin composition include, for example, hydroquinone and hydroquinone monoethyl ether. Examples of antifoaming agents include silicone-based and fluorine-based compounds, and surfactants include anionic, cationic, and nonionic compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition is prepared by uniformly mixing desired amounts of each of the above components. In addition, when the prepared photosensitive resin composition does not contain an insoluble component such as a pigment, it may be filtered using a filter so that the photosensitive resin composition becomes uniform.

<<Method for producing patterned cured film>>
A patterned cured film can be produced by using the photosensitive resin composition described above.
A patterned cured film is typically
Forming a coating film by applying the photosensitive resin composition described above on a substrate;
exposing the coating film,
the coating is patterned, or
It is manufactured by a method in which position-selective exposure is performed on a coating film, and then development is performed on the exposed coating film.

The substrate (substrate or support) can be selected according to various uses, and examples thereof include quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, and metals such as Ni, Cu, Cr, and Fe. Substrates, paper, SOG (Spin On Glass), polymer substrates such as polyester films, polycarbonate films, and polyimide films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulation There are no particular restrictions on the substrate, such as a flexible substrate, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, or the like. Furthermore, for example, in the case of forming a laminated structure on a substrate, any layer which is already formed on the substrate to be a lower structure is also included in the concept of the base material to which the photosensitive resin composition is applied. Also, the shape of the substrate is not particularly limited, and may be plate-like or roll-like. The base material may have unevenness on the surface, for example, according to various patterns. Moreover, as the base material, a light-transmitting or non-light-transmitting base material can be selected.

A method for forming a patterned coating film on a substrate is not particularly limited. When forming a patterned coating film, the patterned coating film is typically formed by a printing method such as an inkjet method or a screen printing method.
When forming a patterned coating film by a printing method, the viscosity of the photosensitive resin composition is preferably adjusted to the optimum viscosity according to the selected printing method. Methods for adjusting the viscosity include dilution with an organic solvent (S) and addition of a viscosity modifier.

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

The coating film is then dried as necessary. A drying method is not particularly limited. As a drying method, for example, (1) a method of drying on a hot plate at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, (2) at room temperature and (3) placing in a warm air heater or an infrared heater for several tens of minutes to several hours to remove the solvent.

A patterned cured film is formed by exposing the patterned coating film.

Light sources for exposure are not particularly limited, and examples thereof include high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, carbon arc lamps, and LEDs. Using such a light source, the coating film is irradiated with ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet ₍ EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, g-ray, i-ray. , h-rays, j-rays, k-rays, or the like, or electromagnetic waves to expose the coating film.

Although the exposure amount varies depending on the composition of the photosensitive resin composition, it is preferably 10 mJ/cm ² or more and 2000 mJ/cm ² or less, more preferably 100 mJ/cm ² or more and 1500 mJ/cm ² or less, and 200 mJ/cm ² or more and 1200 mJ/cm 2 or more. cm ² or less is more preferable. Although the exposure illuminance varies depending on the composition of the photosensitive resin composition, it is preferably in the range of 1 mW/cm ² or more and 50 mW/cm ² or less.

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

On the other hand, when the coating film is subjected to position-selective exposure, a non-patterned coating film is formed on the substrate surface. Typically, the photosensitive resin composition is applied over the entire surface of the substrate, or substantially over the entire surface.
The coating method is not particularly limited. Preferred coating methods include contact transfer coating devices such as roll coaters, reverse coaters, and bar coaters, and non-contact coating devices such as spinners (rotary coating devices), dispensers, inkjets, sprayers, screen printers, and curtain flow coaters. method to be used.
The coating film thus formed may be dried if necessary, similarly to the patterned coating film. The drying method is the same as the method described for the patterned coating film.

The unpatterned coating film formed as described above is subjected to position-selective exposure through a negative mask having a light-transmitting portion having a shape corresponding to the pattern shape of the cured film. .
Except for using a negative mask, the exposure method is the same as the exposure method for the patterned coating film described above.

Then, the exposed coating film is developed with a developer to form a patterned cured film. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

The patterned cured film obtained after development may be heated in the same manner as the above-described patterned coating film is subjected to exposure.

<<Method of Forming a Bank>>
The method of forming the bank using the photosensitive resin composition described above is not particularly limited. Banks are usually formed as partitions for partitioning pixels in optical elements such as color filters, organic EL display elements, quantum dot displays, and organic TFT arrays.
Therefore, in the method of forming the bank, a substrate suitable for each optical element is selected. Also, it is generally preferred that the bank be light-shielding. For this reason, a photosensitive resin composition containing a light shielding agent (E1) as a coloring agent (E) is preferable as the photosensitive resin composition for forming the bank.

The method of forming the bank is the same as the method of producing the patterned cured film described above, except that the substrate is selected according to each optical element. By forming the banks on the substrate for manufacturing the optical element in this way, the substrate with bank for manufacturing the optical element is manufactured.

<<Method for manufacturing an optical element>>
Various optical elements are manufactured using the banked substrate for optical element manufacturing manufactured by the method described above. The method of manufacturing the optical element is not particularly limited. Preferably, after forming a pattern of banks on the substrate by the above method, the optical element is manufactured by injecting ink into regions surrounded by the banks on the substrate to form pixels.

When the banks are formed using the photosensitive resin composition described above, the area surrounded by the banks is suppressed from becoming liquid-repellent. Therefore, the area surrounded by the bank can be sufficiently covered with the ink for pixel formation. As a result, for example, the problem of halation in the organic EL display element can be resolved.

Water, an organic solvent, and a mixed solvent thereof can be used as the solvent used when forming the ink for pixel formation. The organic solvent is not particularly limited as long as it can be removed from the film formed after injecting the ink. Specific examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, and butyl acetate. In addition, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, and the like can be added to the ink.

As a method for injecting ink into the region surrounded by the bank, the ink jet method is preferable because a small amount of ink can be easily injected into a predetermined location. The ink used to form pixels is appropriately selected according to the type of optical element to be manufactured. When the ink is injected by an inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be discharged satisfactorily from the inkjet head. . The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.

The type of optical element is not particularly limited as long as it is an optical element having a bank. Suitable optical elements include color filters, organic EL display elements, quantum dot displays or organic TFT arrays.

Using the optical element manufactured by the method described above, various display devices are manufactured according to known methods.

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

[Examples 1 to 13 and Comparative Examples 1 to 19]

Cardo resins RE1 and RE2 synthesized according to the following method were used as the alkali-soluble resin (A) (component (A)) in Examples and Comparative Examples. RE2 is a resin obtained by reacting a copolymer of 55 mol % benzyl methacrylate and 45 mol % methacrylic acid with 15 mol % of 3,4-epoxycyclohexylmethyl acrylate based on the total structural units of the copolymer. be.

A method for producing a cardo resin as RE1 is described below.
First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were placed in a 500 mL four-necked flask. was charged and heated and dissolved at 90 to 100° C. while blowing air at a rate of 25 mL/min. Next, the solution was gradually heated to 120° C. while the solution was still cloudy and dissolved completely. At this time, the solution gradually became transparent and viscous, but the stirring was continued. During this time, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-obtained bisphenol fluorene type epoxy acrylate and dissolved, and then 80.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. After mixing, the temperature was gradually increased to 110-115° C. for 4 hours to react. After confirming the disappearance of the acid anhydride groups, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain a cardo resin. Disappearance of acid anhydride groups was confirmed by IR spectrum.

Dipentaerythritol hexaacrylate was used as the photopolymerizable monomer (B) (component (B)) in Examples and Comparative Examples.

In the examples and comparative examples, the compounds described below were used as the photopolymerization initiator (C) (component (C)). In the examples, the following PI1 to PI7, which are oxime ester compounds represented by the formula (C1), were used. In Comparative Examples, the following PI8 to PI10, which are oxime ester compounds that do not correspond to the oxime ester compounds represented by the formula (C1), were used.

In Examples and Comparative Examples, a fluororesin containing the following units in the following proportions was used as the fluororesin (D) (component (D)). In the formula below, the lower right number of each unit represents the content (mol%) of each unit in the fluororesin.

In Examples and Comparative Examples, an organic pigment mixed dispersion (C.I. Pigment Blue 15:6/C.I. Pigment Blue 15:6/C.I. Pigment) corresponding to light shielding agent (E1) was used as the colorant (E) (component (E)). Violet 23/C.I. Pigment Red 256=40 mass %/20 mass %/40 mass %, solid content concentration 15 mass %) was used. The amount of the colorant (D) described in Table 1 below is not the amount of the dispersion, but the amount of solid content (amount of pigment and dispersant) in the dispersion.

In Examples and Comparative Examples, the following compounds were used as imidazole generators (F).

Alkali-soluble resin (A) in the type and amount described in Table 1, photopolymerizable monomer (B) in the amount described in Table 1, and photoinitiator (C) of the type described in Table 1 3.5 Parts by mass, 1 part by mass of the fluororesin (D) in the amount shown in Table 1, the colorant (E) in the amount shown in Table 1, and 0.5 parts by weight of the imidazole generator (F), It was uniformly dissolved and dispersed in an organic solvent (S) so that the solid content concentration was 15% by mass to obtain a photosensitive resin composition of each example and comparative example. As the organic solvent (S), a mixed solvent composed of 15% by mass of diethylene glycol methyl ethyl ether and 85% by mass of propylene glycol monomethyl ether acetate was used.

Using the obtained photosensitive resin compositions of each example and comparative example, pixel repellency (liquid repellency of non-patterned area), cross-sectional shape, and methoxybenzene contact angle (cured film Liquid repellency) was evaluated.

[Pixel flipping evaluation]
The photosensitive resin composition was spin-coated on a glass substrate (10 cm×10 cm) and heated at 90° C. for 120 seconds to form a coating film with a thickness of 1.0 μm on the surface of the glass substrate. After that, using a proximity exposure device (product name: TME-150RTO, manufactured by Topcon Corporation), exposure was performed at an exposure amount of 100 mJ/cm ² through a negative mask (10 μm wide, 200 μm square matrix pattern). . The exposed film was developed with a 0.04% by mass KOH aqueous solution at 26° C. for 50 seconds and then baked at 230° C. for 30 minutes to form a matrix pattern.
After dropping methoxybenzene onto the glass substrate on which the matrix pattern was formed, the inside of the matrix was observed with a scanning electron microscope. Next, from the scanning electron microscope image, the area (μm ² ) of the portion (repelled portion) where methoxybenzene was not applied inside the matrix was measured. The ratio (%) of the area (μm ² ) of the repelling portion to the matrix internal area (200×200 μm ² ) was calculated, and the degree of pixel repelling was evaluated based on this ratio (%). Evaluation criteria for pixel flipping are as follows. Table 1 shows the evaluation results of pixel flipping.
○: The ratio of the area of the flipping portion to the internal area of the matrix is 0% or more and less than 5%.
Δ: The ratio of the area of the flipping portion to the internal area of the matrix is 5% or more and less than 20%.
x: The ratio of the area of the flipping portion to the internal area of the matrix is 20% or more.

[Cross-sectional shape evaluation]
The photosensitive resin composition was spin-coated on a glass substrate (10 cm×10 cm) and heated at 90° C. for 120 seconds to form a coating film with a thickness of 1.0 μm on the surface of the glass substrate. After that, using a proximity exposure apparatus (product name: TME-150RTO, manufactured by Topcon Corporation), exposure was performed at an exposure amount of 100 mJ/cm ² through a negative mask (line and space pattern with a width of 10 μm). After exposure, the film was developed in a 0.04% by mass KOH aqueous solution at 26°C for 50 seconds and then baked at 230°C for 30 minutes. ) was measured. Table 1 shows the measured taper angles. Based on the measured taper angle, the cross-sectional shape was evaluated according to the following criteria.
○: 45 degrees or more and 90 degrees or less △: 30 degrees or more and 44 degrees or less ×: 29 degrees or less or 91 degrees or more

[Contact angle]
The photosensitive resin composition was spin-coated on a glass substrate (10 cm×10 cm) and heated at 90° C. for 120 seconds to form a coating film with a thickness of 1.0 μm on the surface of the glass substrate. After that, using a proximity exposure device (product name: TME-150RTO, manufactured by Topcon Corporation), exposure was performed at an exposure amount of 100 mJ/cm ² . 50 μL of methoxybenzene was dropped on the film surface after exposure, and the contact angle was measured using DROP MASTER-700. A case where the contact angle was 50°C or more was evaluated as ◯, and a case where the contact angle was less than 50°C was evaluated as x.

According to Table 1, it contains an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a fluororesin (D), and is represented by the above formula (C1). When the photosensitive resin composition of the example containing the photopolymerization initiator (C-I), which is an oxime ester compound having a structure of It can be seen that the expression of sexuality can be suppressed.
In addition, the patterned cured film formed using the photosensitive resin composition of the example exhibits a taper angle within a range suitable for a bank for manufacturing an optical element, and also contains an organic solvent such as methoxybenzene. It had a liquid repellency of about.

On the other hand, the photopolymerization initiator (C-I), which is an oxime ester compound having the structure represented by the above formula (C1) and which contains the fluorine-based resin (D), which is a liquid-repellent component, is added to the photopolymerization initiator (C ), it is found that when the photosensitive resin composition of the comparative example that does not contain ) is used, a large amount of pixel rejection occurs, and it is difficult to suppress the development of liquid repellency in the non-pattern area.
In addition, the patterned cured film formed using the photosensitive resin composition of Comparative Example exhibited a low taper angle unsuitable as a bank for manufacturing optical elements, and the organic solvent such as methoxybenzene In some cases, the liquid repellency of the liquid was low.

Claims (16)

A photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a fluororesin (D) ,
The alkali-soluble resin (A) contains a resin (a-1) having a cardo structure,
The photopolymerization initiator (C) has the following formula (C1):

(In the formula (C1), X ⁰¹ is represented by the following formulas (C1-1a) to (C1-1c):

is a monovalent or divalent group represented by any one of , X ⁰² and X ⁰³ are each independently a monovalent organic group, X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, a substituent an alkyl group having 1 to 11 carbon atoms which may have or an aryl group which may have a substituent; at least one is 1;
In formulas (C1-1a) to (C1-c), X ⁰⁶ is an aromatic group optionally having a monovalent substituent bonded to the nitrogen atom in the carbazole ring via a C—N bond,
X ⁰⁹ is a divalent aromatic group that binds to the nitrogen atom in the carbazole ring via a C—N bond, and among the two bonds of X ⁰⁹ , formula (C1-1a) and formula (C1-1c ) is bonded to the carbon atom constituting the aromatic ring contained in X ⁰⁹ ,
The wavy line in formulas (C1-1a) to (C1-c) represents a bonding site with a group when at least one of t2 and t3 is 1,
X ⁰⁷ and X ⁰⁸ are each independently a nitro group, an optionally substituted aroyl group, or an optionally substituted heteroaroyl group; t4 and t5 are each independently 0 or 1; is. )
A photosensitive resin composition comprising a photopolymerization initiator (C-I) represented by. The photosensitive resin composition according to claim 1, wherein the sum of t2 and t3 is 1, and the sum of t4 and t5 is 1 or 2. Furthermore, the photosensitive resin composition of any one of Claim 1 or 2 containing a coloring agent (E). 4. The photosensitive resin composition according to claim 3, wherein the coloring agent (E) is a light shielding agent (E1). 5. The photosensitive resin composition according to claim 4, which is used for bank formation. Forming a coating film by applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate;
exposing the coating film,
the coating is patterned, or
A method for producing a patterned cured film, wherein the coating film is subjected to position-selective exposure, and then the exposed coating film is developed. A patterned cured film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 5. A bank comprising a cured product of the bank-forming photosensitive resin composition according to claim 5 . A banked substrate for manufacturing an optical element, comprising the bank according to claim 8 on the substrate. An optical element comprising the banked substrate for manufacturing an optical element according to claim 9 . A display device comprising the optical element according to claim 10 . Coating the photosensitive resin composition according to claim 5 on a substrate to form a coating film;
exposing the coating film,
the coating is patterned, or
A method of forming a bank, wherein the coating film is subjected to position-selective exposure, and then the exposed coating film is developed. 13. A method for manufacturing an optical element, comprising injecting ink into a region surrounded by the bank formed on the substrate by the method according to claim 12 to form a pixel. 14. The method of manufacturing an optical element according to claim 13, wherein the ink is injected into the area surrounded by the bank by an inkjet method. 15. The method for manufacturing an optical element according to claim 13, wherein said optical element is a color filter, an organic EL display element, a quantum dot display, or an organic TFT array. Claims 1 to 4, wherein the fluororesin (D) is a copolymer obtained by copolymerizing at least (d1) a monomer having an ethylenically unsaturated group and a fluorine atom and (d2) (meth)acrylic acid. The photosensitive resin composition according to any one of the above.