JP6886782B2 - A photosensitive resin composition, a cured film, a bank for partitioning a light emitting layer in an organic EL element, a substrate for an organic EL element, an organic EL element, a method for producing a cured film, a method for producing a bank, and a method for producing an organic EL element. - Google Patents

Description

The present invention comprises a photosensitive resin composition capable of forming a cured film with a small amount of generated gas, a cured film formed by using the above-mentioned photosensitive resin composition, and a bank for partitioning a light emitting layer in an organic EL element. A substrate and an organic EL element for an organic EL element having the above-mentioned bank, a method for manufacturing a bank for partitioning a light emitting layer in a cured film and an organic EL element using the above-mentioned photosensitive resin composition, and the above-mentioned bank are provided. The present invention relates to a method for manufacturing an organic EL element using a substrate for an organic EL element.

Conventionally, optical elements such as organic EL display elements, color filters, and organic TFT arrays have various functional layers in a region surrounded by banks after forming a bank (partition wall) surrounding pixels on a substrate. It is manufactured by providing. As a method for easily forming such a bank, a method for forming a bank by a photolithography method using a photosensitive resin composition is known (see Patent Document 1 and Patent Document 2).

JP-A-2009-204805 International Publication No. 2013/067789 Pamphlet

However, when a cured film that can be used as a bank is formed according to the methods described in Patent Documents 1 and 2, there is a concern that the amount of gas generated from the cured film will increase. In the organic EL element, the bank is provided so as to be in contact with an electrode layer such as ITO or a light emitting layer. Then, if the electrode layer and the light emitting layer are contaminated with the gas generated from the bank, there is a concern that these deteriorations will be promoted.
Therefore, a photosensitive resin composition capable of forming a cured film with a small amount of generated gas is desired.

The present invention has been made in view of the above problems, and is a photosensitive resin composition capable of forming a cured film having a small amount of generated gas, and a cured film and an organic substance formed by using the above-mentioned photosensitive resin composition. A bank for partitioning a light emitting layer in an EL element, a substrate and an organic EL element for an organic EL element having the above-mentioned bank, and a curing film using the above-mentioned photosensitive resin composition and a partition for a light emitting layer in the organic EL element. It is an object of the present invention to provide a method for manufacturing a bank of the above, and a method for manufacturing an organic EL device using a substrate for an organic EL device provided with the above-mentioned bank.

The present inventors have a polyfunctional crosslinkability having an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a plurality of epoxy groups or oxetanyl groups in one molecule. In the photosensitive resin composition containing the compound (D), the alkali-soluble resin (A) contains a resin having a cardo skeleton, and the polyfunctional crosslinkable compound (D) has an epoxy equivalent or an oxetanyl equivalent of 50 to 350 g / eq. It has been found that the above-mentioned problems can be solved by using the above-mentioned compound, and the present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention includes an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a plurality of epoxy groups or oxetanyl groups in one molecule. Including the functionally crosslinkable compound (D)
The alkali-soluble resin (A) contains a resin having a cardo skeleton and contains.
A photosensitive resin composition having an epoxy equivalent or an oxetanyl equivalent of the polyfunctional crosslinkable compound (D) of 50 to 350 g / eq.

A second aspect of the present invention is a cured film obtained by curing the photosensitive resin composition according to the first aspect.

A third aspect of the present invention is the photosensitive resin composition according to the first aspect, which is obtained by curing a photosensitive resin composition used for forming a bank for partitioning a light emitting layer in an organic EL element. , A bank for partitioning a light emitting layer in an organic EL element.

A fourth aspect of the present invention is a substrate for an organic EL device including the bank according to the third aspect.

A fifth aspect of the present invention is an organic EL device including the bank according to the third aspect.

A sixth aspect of the present invention includes a step of forming a coating film by applying the photosensitive resin composition according to the first aspect.
The process of exposing the coating film and
This is a method for producing a cured film, which comprises a step of curing the exposed coating film.

A seventh aspect of the present invention is a method of manufacturing a bank for partitioning a light emitting layer in an organic EL element on a substrate.
A coating film is formed on a substrate by applying the photosensitive resin composition according to the first aspect, which is used for forming a bank for partitioning a light emitting layer in an organic EL element. Process and
A process of regioselectively exposing a portion of the coating film corresponding to the position of the bank,
The process of developing the exposed coating film and
It is a method including a step of curing the developed coating film.

An eighth aspect of the present invention is a method for manufacturing an organic EL element, which comprises a step of forming a light emitting layer in a region partitioned by a bank in the substrate for the organic EL element according to the fourth aspect.

According to the present invention, a photosensitive resin composition capable of forming a cured film with a small amount of generated gas, a cured film formed by using the above-mentioned photosensitive resin composition, and a bank for partitioning a light emitting layer in an organic EL element. A method for manufacturing a substrate and an organic EL element for an organic EL element having the above-mentioned bank, a method for manufacturing a bank for partitioning a light emitting layer in the cured film and the organic EL element using the above-mentioned photosensitive resin composition, and the above-mentioned bank. It is possible to provide a method for manufacturing an organic EL element using a substrate for the organic EL element provided with the above.

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

<< Photosensitive resin composition >>
The photosensitive resin composition is a polyfunctional crosslink containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a plurality of epoxy groups or oxetanyl groups in one molecule. Includes sex compound (D).
The alkali-soluble resin (A) includes a resin having a cardo skeleton.
The epoxy equivalent or oxetanyl equivalent of the polyfunctional crosslinkable compound (D) is 50-350 g / eq.
The photosensitive resin composition having the above structure can form a cured film in which gas generation is suppressed.
Hereinafter, essential or arbitrary components of the photosensitive resin composition and a method for preparing the photosensitive resin composition will be described.

<Alkali-soluble resin (A)>
The photosensitive resin composition contains an alkali-soluble resin (A) (also referred to as “component (A)” in the present specification). The alkali-soluble resin (A) includes a resin having a (A1) cardo structure (hereinafter, also referred to as "(A1) cardo resin").
Here, in the present 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.) having alkali solubility in the molecule.

The fact that the photosensitive resin composition of the present embodiment can form a cured film in which gas generation is suppressed is considered to have the following effects, although it is not clear.
That is, first, the (A1) cardo resin has a bulky cardo structure.
On the other hand, when forming a cured film using the photosensitive resin composition, the (A1) cardo resin and the polyfunctional crosslinkable compound (D) having a plurality of epoxy groups or oxetanyl groups in one molecule are used. Cross-linking occurs between them.
Combined with these effects, when a cured film is formed using a photosensitive resin composition, when a laminated structure including a cured film of a photosensitive resin composition is processed to form various elements, and when a photosensitive resin is formed. It is considered that the generation of gas from the cured film is suppressed when various elements including the cured film of the composition are used.

The resin having the (A1) cardo skeleton is not particularly limited as long as it is a resin having a predetermined alkali solubility. The cardo skeleton is a skeleton in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. The second annular structure and the third annular structure may have the same structure or different structures.
A typical example of a cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to a carbon atom at the 9-position of the fluorene ring.

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

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

In the above formula (a-2), ^Ra1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and ^Ra2 independently represents a hydrogen atom or a methyl group. , ^{R a3} each independently represent an alkylene group of straight or branched chain, m2 is ^{W a} represents 0 or 1, a group represented by the following formula (a3).

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

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

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

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

In the formula (a-2a), ^Ra1 , ^Ra2 , ^Ra3 , and m2 are as described in the formula (a-2). The ring A in the formula (a-2a) is as described in the formula (a-3).

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

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

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

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

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

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

^{The alkyl group that can be selected as Ra4} in the formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms contained in the alkyl group in this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms thereof is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and 1 to 3 from the viewpoint that a cardo resin having excellent heat resistance can be easily obtained. Is particularly preferable.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

^{As R a4} in the formula (a-4), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable independently from the viewpoint that a cardo resin having excellent heat resistance can be easily obtained. ^{R a4} in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
^{The plurality of Ra4s} in the formula (a-4) are preferably the same group because it is easy to prepare a high-purity tetracarboxylic dianhydride.

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

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

Examples of the tetracarboxylic acid dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-Tetracarboxylic acid dianhydride (also known as "norbornane-2-spir-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5'', 6,6'' -Tetracarboxylic acid dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane) -5,5", 6,6 "-tetra Norbornane dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (also known as "norbornane-" 2-Spiro-2'-Cyclohexanone-6'-Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid dianhydride"), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''- (methylnorbornane) -5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopropanol-α'- Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2''-norbornane-5, 5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2''-norbornane-5,5'', 6,6' '-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride , Norbornane-2-spiro-α-cyclononanonone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclodecanone -Α'-Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2' '-Norbornane-5,5'', 6,6''-Tetracarboxylic acid dianhydride, Norbornane-2-spiro-α-cyclododecanone-α'-Spyro-2''-norbornane-5,5' ', 6, 6''-Tetracarboxylic acid dianhydride, Norbornane Nan-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- Cyclotetradecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α' -Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'-spiro-2' '-Norbornane-5,5'', 6,6''-Tetracarboxylic acid dianhydride, Norbornane-2-spiro-α- (methylcyclohexanone) -α'-Spiro-2''-norbornane-5,5 '', 6,6''-Tetracarboxylic acid dianhydride and the like can be mentioned.

The weight average molecular weight of the (A1) cardo resin is preferably 1000 to 40,000, more preferably 2000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

The alkali-soluble resin (A) may contain an alkali-soluble resin other than the (A1) cardo resin. Examples of such an alkali-soluble resin include (A2) acrylic resins.

As the (A2) acrylic resin, a resin containing a structural unit derived from (meth) acrylic acid and / or a structural unit derived from (meth) acrylic acid ester is used. The (meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester is represented by the following formula (a-5), and is not particularly limited as long as the object of the present invention is not impaired.

In the above formula (a-5), R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. This organic group may contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be linear, branched or cyclic.

The substituent other than a hydrocarbon group in the organic group R ^a8, the effect is not particularly limited as long as they do not impair the present invention, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkyl thioether group, aryl ether group, aryl thioether group, amino group (-NH ₂ , -NHR, -NRR': R and R'independently indicate a hydrocarbon group) and the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched or cyclic.

R ^a8 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. When these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

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

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

Further, the (A2) acrylic resin may be obtained by further polymerizing a compound other than (meth) acrylic acid and (meth) acrylic acid ester. Examples of such other compounds include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more.

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

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

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

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

Examples of vinyl esters include vinyl butyrate, vinylisobutyrate, vinyltrimethylacetate, vinyldiethylacetate, vinylvalate, vinylcaproate, vinylchloracetate, vinyldichloroacetate, vinylmethoxyacetate, vinylbutoxyacetate, and vinylfu. Examples thereof include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

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

The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from (meth) acrylic acid ester in the (A2) acrylic resin are not particularly limited as long as the object of the present invention is not impaired. .. The amount of the structural unit derived from (meth) acrylic acid in the (A2) acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the mass of the acrylic resin. The amount of the structural unit derived from the (meth) acrylic acid ester in the (A2) acrylic resin is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, based on the mass of the acrylic resin. ..

The total of the amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from (meth) acrylic acid ester in the (A2) acrylic resin is particularly large as long as the object of the present invention is not impaired. Although not limited, it is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, based on the mass of the (A2) acrylic resin.

The weight average molecular weight of the (A2) acrylic resin is preferably 2000 to 20000, more preferably 5000 to 30000. Within the above range, the film-forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

The ratio of the mass of the (A1) cardo resin to the mass of the alkali-soluble resin (A) 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. It is particularly preferable, and 100% by mass is most preferable.

The content of the alkali-soluble resin (A) is preferably 20 to 85% by mass, preferably 25 to 75% by mass, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. More preferably. Within the above range, a cured film that does not easily generate gas can be formed, and a photosensitive resin composition having excellent developability can be easily obtained.

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

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

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

Among these monomers having ethylenically unsaturated groups, a polyfunctional monomer having three or more functionalities tends to increase the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing. Is preferable, a polyfunctional monomer having four or more functionalities is more preferable, and a polyfunctional monomer having five or more functionalities is further preferable.

The content of the photopolymerizable monomer (B) in the composition is preferably 1 to 50% by mass, preferably 5 to 40% by mass, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. % Is more preferable. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

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

Specifically, as the photopolymerization initiator (C), 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime), (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1) -Methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide , 4-Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2- Ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (O-ethoxycarbonyl) oxime, o- Methyl benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-Methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumenehydroperoxide, 2 -Mercaptobe Nzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone , P-Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, Pentyl-4-dimethylaminobenzoate, 9-phenylaclysine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) Propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methyl) Phenyl-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (tric) Loromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4) -Methoxy) Phenyl-s-Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-) Bromo-4-methoxy) styrylphenyl-s-triazine and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

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

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

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

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

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

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 6 carbon atoms. When R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

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

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

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10 carbon atoms. When R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14 carbon atoms. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, ^Rc1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indol, Examples thereof include isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxalin. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

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

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

Among R ^c1 , alkyl groups having 1 to 6 carbon atoms and 1 to 1 carbon atoms have an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms because they are chemically stable, have few steric obstacles, and facilitate the synthesis of an oxime ester compound. A group selected from the group consisting of an alkoxy group of 6 and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

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

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

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

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

Specific examples of the substituent which the phenyl group or the carbazolyl group may have are an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. For phenylalkyl groups which may have groups, naphthylalkyl groups which may have substituents, heterocyclyl groups which may have substituents, and amino groups substituted with one or two organic groups. , R ^c1 .

In R ^c2 , an alkyl group having 1 to 6 carbon atoms is an example of a substituent when the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent. An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group. Naftyl group; benzoyl group; naphthoyl group; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Group; Monoalkylamino group having an alkyl group with 1 to 6 carbon atoms; Dialkylamino group with an alkyl group with 1 to 6 carbon atoms; Morphorin-1-yl group; Piperazin-1-yl group; Halogen; Nitro Group; cyano group can be mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 to 4 are preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

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

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

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

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

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

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

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

^{R c5} in the formula (c3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ^c5 are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. An alkoxycarbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a carbon atom number 7 which may have a substituent. It may have a phenylalkyl group of ~ 20, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent. Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

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

^{R c6} in the formula (c3) is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of a group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Heterocyclyl groups may be mentioned. Among these groups, a phenyl group which may have a substituent is more preferable as R ^{c6, and a 2-methylphenyl group is particularly preferable.}

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms and 1 to 1 carbon atoms. An alkoxy group of 6, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl having 1 to 6 carbon atoms. Examples thereof include a monoalkylamino group having a group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 to 4 are preferable. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 has a plurality of substituents, the plurality of substituents may be the same or different.

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

The oxime ester compound represented by the formula (c1) can be synthesized, for example, according to the following scheme 1 when p is 0. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated by a Friedercrafts reaction using a halocarbonyl compound represented by the following formula (c1-2), and the following formula is used. A ketone compound represented by (c1-3) was obtained, and the obtained ketone compound (c1-3) was oximeized with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), followed by the formula. The hydroxy group in the oxime compound of (c1-4) can be acylated to obtain an oxime ester compound represented by the following formula (c1-7). Examples of the acylating agent include acid anhydrides ((R ^c3 CO) ₂ O) represented by the following formula (c1-5) or acid halides (R ^c3 COHal, Hal) represented by the following formula (c1-6). Is a halogen.) Is preferably used. In the following formula (c1-2), H is a halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4), and (c1-7). , R ^c1 , R ^c2 , R ^c3 , and n1 are the same as in equation (c1).

<Scheme 1>

The oxime ester compound represented by the formula (c1) can be synthesized, for example, according to the following scheme 2 when n2 is 1. Specifically, the ketone compound represented by the following formula (c2-1) is nitrite ester represented by the following formula (c2-2) in the presence of hydrochloric acid (RONO and R have 1 to 6 carbon atoms). The alkyl group of.) Is reacted to obtain a ketooxime compound represented by the following formula (c2-3), and then the hydroxy group in the ketooxime compound represented by the following formula (c2-3) is acylated. An oxime ester compound represented by the following formula (c2-6) can be obtained. As the acylating agent, an acid anhydride represented by the following formula (c2-4) ((R ^c3 CO) ₂ O) or an acid halide represented by the following formula (c2-5) (R ^c3 COHal, Hal) Is a halogen.) Is preferably used. In the following formulas (c2-1), (c2-3), (c2-4), (c2-5), and (c2-6), R ^c1 , R ^c2 , R ^c3 , and n1 are formulas. It is the same as (c1).

<Scheme 2>

Further, in the oxime ester compound represented by the formula (c1), n2 is 1, R ^c1 is ^{a methyl group, and R c1} is paralyzed with respect to the methyl group bonded to the benzene ring to which ^{R c1 is bonded.} In the case of binding to the position, for example, the compound represented by the following formula (c2-7) can be synthesized by oximeization and acylation in the same manner as in Scheme 1. In the following formula (c2-7), R ^c2 is the same as the formula (c1).

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

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

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

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

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

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

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

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

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

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. When R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples thereof include an n-decyl group and an isodecyl group. When R ^c7 is an alkyl group, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. When R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c7 is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

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

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

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where R ^c7 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

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

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

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

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

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c7} further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having a number of 2 to 7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. , Dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c7} further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When ^{the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c7} have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, as R ^c7 , a nitro group or ^{a group represented by R c12-} CO- tends to improve the sensitivity and is preferable. R ^c12 is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. A good heterocyclyl group is mentioned. Among these groups, 2-methylphenyl group, thiophen-2-yl group, and α-naphthyl group are particularly preferable as R ^c12.
Further, when R ^c7 is a hydrogen atom, the transparency tends to be good, which is preferable. If R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.

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

When R ^c8 and R ^c9 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of cases where R ^c8 and R ^c9 are chain alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl group, Isopentyl group, sec-Pentyl group, tert-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Examples include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ^c8 and R ^c9 are alkyl groups, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

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

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

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

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

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

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

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

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

Examples of suitable groups among ^{R c8} and R ^c9 described above include groups represented by the ^{formula −A 1} −A ^2. In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

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

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

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

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

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

^As the ^{R c10,} a group represented by -A 3 ^{-CO-O-A 4} are also preferred. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

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

Preferred examples of A ⁴ is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific preferable examples of A ⁴ is methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group and the like.

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

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０〜４の整数であり、Ｒ^ｃ１３及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１〜８の整数であり、ｎ８は１〜５の整数であり、ｎ９は０〜（ｎ８＋３）の整数であり、Ｒ^ｃ１５は有機基である。） ^Having described ^{R c10,} as the ^{R c10,} preferably a group represented by the following formula (C4a) or (C4b).

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

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

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

In the above formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (c4b), n9 is 0 to (n8 + 3), an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is particularly preferable. In the above formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Examples of the substituent that R ^c11 may have when it is an alkyl group include a phenyl group and a naphthyl group. Further, ^{as the substituent which may be possessed when R c7} is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In the formula (c4), as R ^c11 , a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified. Of these, a methyl group or a phenyl group is more preferable.

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

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

The compound represented by the general formula (c4) can be synthesized, for example, according to the following scheme 3 when n5 is 0. In Scheme 3, a fluorene derivative represented by the following formula (c3-1) is used as a raw material. When R ^c7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (c3-1) is replaced with a fluorene derivative in which the 9-position is ^{substituted with R c8} and R ^c9 by a well-known method. It can be obtained by introducing a substituent R ^c7. The fluorene derivative in which the 9-position is ^{substituted with R c8} and R ^c9 is, for example, an alkali metal hydroxide as described in JP-A-06-234668 when ^{R c8} and R ^{c9 are alkyl groups.} It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. Further, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By carrying out the alkylation reaction, 9,9-alkyl substituted fluorene can be obtained.

^{An acyl group represented by -CO-R c10} is introduced into the fluorene derivative represented by the formula (c3-1) by a Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (c3-3) is obtained. can get. The acylating agent for introducing an acyl group represented by -CO-R ^{c10 may be a halocarbonyl compound or an acid anhydride.} As the acylating agent, a halocarbonyl compound represented by the formula (c3-2) is preferable. In formula (c3-2), H is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction or by protecting and deprotecting other positions at the acylated position. it can.

^{Next, the group represented by -CO-R c10} in the obtained fluorene derivative represented by the formula (c3-3) is converted into a group represented by -C (= N-OH) -R ^c10. The oxime compound represented by the formula (c3-4) is obtained. The method for converting the group represented by -CO-R ^c10 to the group represented by -C (= N-OH) -R ^c10 is not particularly limited, but oxime formation with hydroxylamine is preferable. The oxime compound of the formula (c3-4) and the acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5), or the acid halide represented by the following formula (c3-6) ( R ^c11 COHal and Hal are halogen atoms.) To obtain a compound represented by the following formula (c3-7).

In the formulas (c3-1), (c3-2), (c3-3), (c3-4), (c3-5), (c3-6), and (c3-7), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 are the same as in the formula (c4).

^{Further, in Scheme 3, R c10} contained in each of the formula (c3-2), the formula (c3-3), and the formula (c3-4) may be the same or different. ^{That is, R c10} in the formulas (c3-2), formula (c3-3), and formula (c3-4) may undergo chemical modification in the synthetic process represented as Scheme 3. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. The ^{chemical modifications that R c10} may undergo are not limited to these.

<Scheme 3>

The compound represented by the formula (c4) can be synthesized, for example, according to the following scheme 4 when n5 is 1. In Scheme 4, a fluorene derivative represented by the following formula (c4-1) is used as a raw material. Table fluorene derivative represented by the formula (C4-1) carries out the same method as in Scheme 3, the compound represented by the formula (c3-1), with _-CO-CH ^{2 -R c10} by Friedel-Crafts reaction It is obtained by introducing the acyl group to be used. As the acylating agent, a carboxylic acid halide represented by the formula (c3-8): Hal-CO-CH _2- R ^{c10 is preferable. Next, the methylene group existing between the R c10} and the carbonyl group in the compound represented by the formula (c4-1) is oxime-ized to obtain the keto-oxime compound represented by the following formula (c4-3). The method for oxime-forming the methylene group is not particularly limited, but in the presence of hydrochloric acid, a nitrite ester represented by the following general formula (c4-2) (RONO and R are alkyl groups having 1 to 6 carbon atoms) is used. The method of reacting is preferable. Next, the ketooxime compound represented by the following formula (c4-3) and the acid anhydride (R ^c11 CO) ₂ O) represented by the following formula (c4-4), or the following formula (c4-5). The compound represented by the following formula (c4-6) can be obtained by reacting with the acid halide (R ^{c11 COHal, Hal is a halogen atom).} In the following formulas (c4-1), (c4-3), (c4-4), (c4-5), and (c4-6), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 is the same as the equation (c4).
When n5 is 1, there is a tendency that the generation of foreign substances in the pattern formed by using the photosensitive resin composition containing the compound represented by the formula (c4) can be further reduced.

^{Further, in Scheme 4, R c10} contained in each of the formula (c3-8), the formula (c4-1), and the formula (c4-3) may be the same or different. ^{That is, R c10} in formulas (c3-8), formula (c4-1), and formula (c4-3) may undergo chemical modification in the synthetic process represented as Scheme 4. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. The ^{chemical modifications that R c10} may undergo are not limited to these.

<Scheme 4>

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

The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, preferably 1 to 20% by mass, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. More preferably, it is by mass%. By setting the content of the photopolymerization initiator (C) in the above range, it is possible to obtain a photosensitive resin composition in which defects in the pattern shape are unlikely to occur.

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

<Polyfunctional crosslinkable compound (D)>
The photosensitive resin composition contains a polyfunctional crosslinkable compound (D). The polyfunctional crosslinkable compound (D) is a crosslinkable compound having a plurality of epoxy groups or oxetanyl groups in one molecule.
The epoxy equivalent or oxetanyl equivalent of the polyfunctional crosslinkable compound (D) is 50 to 350 g / eq.
When the photosensitive resin composition contains a polyfunctional crosslinkable compound having an epoxy equivalent or an oxetanyl equivalent in such a range, an alkali-soluble resin (A) is formed when a cured film is formed using the photosensitive resin composition. ) Is densely crosslinked, and it is easy to suppress the generation of gas from the cured film.
Further, from the viewpoint of more remarkably expressing such an effect, the epoxy equivalent or oxetanyl equivalent of the polyfunctional crosslinkable compound (D) is more preferably 60 to 320 g / eq, and more preferably 70 to 300 g / eq. Is even more preferable, and 75 to 280 g / eq is particularly preferable.

From the viewpoint of cross-linking reactivity when forming a cured film, the polyfunctional cross-linking compound (D) preferably contains an epoxy compound having two or more epoxy groups per molecule, and three or more epoxides per molecule. More preferably, it contains an epoxy compound having a group.
The content of the epoxy compound having two or more epoxy groups per molecule in the polyfunctional crosslinkable compound (D) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. It is preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.

The polyfunctional crosslinkable compound (D) includes a polyfunctional epoxy compound or a polyfunctional oxetane compound conventionally blended in various curable compositions as long as the epoxy equivalent or oxetane equivalent is within a predetermined range. Can be used.
The molecular weight of the polyfunctional epoxy compound or the polyfunctional oxetane compound contained in the polyfunctional crosslinkable compound (D) is not particularly limited as long as the object of the present invention is not impaired. The molecular weight of the polyfunctional epoxy compound or polyfunctional oxetane compound is preferably 5000 or less, more preferably 4500 or less, and more preferably 4000 or less, because there are few steric obstacles and it is easy to efficiently crosslink the molecular chains of the alkali-soluble resin (A). The following are particularly preferred.
The lower limit of this molecular weight is not particularly limited, but is, for example, 150 or more.

The polyfunctional crosslinkable compound (D) may be a compound containing an aromatic group or a compound not containing an aromatic group. The polyfunctional crosslinkable compound (D) is preferably a compound containing no aromatic group because it is easy to obtain a photosensitive resin composition capable of forming a cured product with less gas generation.

An example of a suitable polyfunctional crosslinkable compound (D) is a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group. Specific examples of such an alicyclic epoxy compound include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane and bis (3,4-epoxycyclohexylmethyl). Adipate, Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone-modified 3 , 4-Epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3 , 4-Epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylene glycol di (3,4-epoxycyclohexanemethyl) ether, ethylenebis (3,4-) (Epoxycyclohexanecarboxylate), polyfunctional epoxy compounds having a tricyclodecene oxide group, and compounds represented by the following formulas (d1-1) to (d1-5) can be mentioned.
These alicyclic epoxy compounds may be used alone or in combination of two or more.

（式（ｄ１−１）中、Ｚは単結合又は連結基（１以上の原子を有する二価の基）を示す。Ｒ^ｄ１〜Ｒ^ｄ１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In formula (d1-1), Z represents a single bond or a linking group (a divalent group having one or more atoms). R ^{d1 to} R ^d18 are independently hydrogen atom, halogen atom, and organic, respectively. A group selected from the group consisting of groups.)

Examples of the linking group Z include divalent hydrocarbon groups, -O-, -O-CO-, -S-, -SO-, _{-SO 2- , -CBr 2-} , and -C (CBr ₃ ) _2. ^{Examples thereof include} a divalent group selected from the group consisting of −, −C (CF ₃ ) ₂₋ , and −R a19 −O—CO−, and a group to which a plurality of these are bonded.

Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group and the like. .. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Examples thereof include a cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

R ^d19 is an alkylene group having 1 to 8 carbon atoms, and is preferably a methylene group or an ethylene group.

(In the formula (d1-2), R ^{d1 to} R ^d12 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

（式（ｄ１−３）中、Ｒ^ｄ１〜Ｒ^ｄ１０は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ｄ２及びＲ^ｄ８は、互いに結合してもよい。）

(In the formula (d1-3), R ^{d1 to} R ^d10 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^d2 and R ^d8 may be bonded to each other. )

（式（ｄ１−４）中、Ｒ^ｄ１〜Ｒ^ｄ１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ｄ２及びＲ^ｄ１０は、互いに結合してもよい。）

(In the formula (d1-4), R ^{d1 to} R ^d12 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^d2 and R ^d10 may be bonded to each other. )

（式（ｄ１−５）中、Ｒ^ｄ１〜Ｒ^ｄ１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In the formula (d1-5), R ^{d1 to} R ^d12 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

Wherein (d1-1) ~ ^(d1-5), when R ^{a1 to R a18} is an organic group, the organic group is not particularly limited within a range not inhibiting the object of the present invention, it is a hydrocarbon radical , A group consisting of a carbon atom and a halogen atom, or a group containing a heteroatom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom together with a carbon atom and a hydrogen atom. .. Examples of halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.

Examples of the organic group include a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom, and a halogen atom, a carbon atom, and a hydrogen atom. , An oxygen atom, and a group consisting of a halogen atom are preferable. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. , N-Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group , N-Heptadecyl group, n-octadecyl group, n-nonadesyl group, n-icosyl group and other chain alkyl groups; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; phenyl group , O-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group, And aryl groups such as phenanthryl groups; aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group and β-naphthylethyl group can be mentioned.

Specific examples of the halogenated hydrocarbon group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2. , 2-Trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Chain alkyl group halides such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And cycloalkyl halide groups such as 4-bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group. , 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl Group, aryl halide such as 4-fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl It is a halogenated aralkyl group such as a methyl group, a 2-fluorophenylmethyl group, a 3-fluorophenylmethyl group, and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom are hydroxy chains such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl group; Cycloalkyl halide group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 Hydroxyaryl groups such as −dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group. Hydroxyaralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy Group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy Group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, Chain alkoxy groups such as n-nonadesyloxy group and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy Group and chain alkenyloxy group such as 3-n-butenyloxy group; phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4 Aryloxy groups such as −yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, Aralkyloxy groups such as β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethi Lu group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl Ekalkalkyl groups such as groups, 4-methoxy-n-butyl groups, 4-ethoxy-n-butyl groups, and 4-n-propoxy-n-butyl groups; methoxymethoxy groups, ethoxymethoxy groups, n-propoxymethoxy groups. , 2-Methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, Alkoxyalkoxy groups such as 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; 2-methoxyphenyl group, 3-methoxyphenyl group, and 4- An alkoxyaryl group such as a methoxyphenyl group; an alkoxyaryloxy group such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, and a hexanoyl group. An aliphatic acyl group such as a group, a heptanoyle group, an octanoyl group, a nonanoyl group, and a decanoyyl group; an aromatic acyl group such as a benzoyl group, an α-naphthoyl group, and a β-naphthoyl group; -Propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyl Chain alkyloxycarbonyl groups such as oxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups, α-naphthoxycarbonyl groups, and β-naphthoxycarbonyl groups; formyloxy groups, acetyloxy groups, propionyloxy groups, pigs An aliphatic acyloxy group such as a noyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoiloxy group, an octanoyloxy group, a nonanoyloxy group, and a decanoyloxy group; a benzoyloxy group, an α-naphthoyloxy group, And aromatic acyloxy groups such as β-naphthoyloxy group.

R ^{d1 to} R ^d18 are preferably groups independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, particularly mechanically. curing film since easily forming excellent in characteristics, the R ^a1 to R ^a18 are all hydrogen atoms is more preferred.

Wherein ^{(d1-2) ~ (d1-5),} R d1 ~R d12 is the same as ^R d1 ^{to R d12} in formula (d1-1). In the formulas (d1-2) and (d1-4), examples of the ^{divalent group formed when R d2} and R ^d10 are bonded to each other include -CH _2- and -C (CH ₃ ). ₂ − can be mentioned. In the formula (P1-3), examples of the ^{divalent group formed when R d2} and R ^d8 are bonded to each other include −CH ₂ − and −C (CH ₃ ) ₂ −.

Among the alicyclic epoxy compounds represented by the formula (d1-1), specific examples of suitable compounds are the following formulas (d1-1a), formula (d1-1b), and formula (d1-1c). Examples include the alicyclic epoxy compound represented, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane [= 2,2-bis (3,4-epoxycyclohexyl) propane], and the like. it can.

Among the alicyclic epoxy compounds represented by the formula (d1-2), specific examples of suitable compounds are bicyclononadeene epoxides represented by the following formula (d1-2a) or dicyclononadeene epoxides. And so on.

Among the alicyclic epoxy compounds represented by the formula (d1-3), specific examples of suitable compounds include S spiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6. , 2'-Oxylan] and the like.

Among the alicyclic epoxy compounds represented by the formula (d1-4), specific examples of suitable compounds include 4-vinylcyclohexenedioxide, dipentenedioxide, limonene dioxide, and 1-methyl-4- (3-). Methyloxylan-2-yl) -7-oxabicyclo [4.1.0] heptane and the like can be mentioned.

Among the alicyclic epoxy compounds represented by the formula (d1-5), specific examples of suitable compounds include 1,2,5,6-diepoxycyclooctane and the like.

Examples of epoxy compounds other than the alicyclic epoxy compound described above that can be suitably used as the polyfunctional crosslinkable compound (D) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Bifunctional epoxy resins such as bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin , And novolak epoxy resin such as bisphenol AD novolak type epoxy resin; ring-type aliphatic epoxy resin such as epoxidized product of dicyclopentadiene type phenol resin; aromatic epoxy resin such as epoxidized product of naphthalene type phenol resin; 9,9- Bis [4- (glycidyloxy) phenyl] -9H-fluorene, 9,9-bis [4- [2- (glycidyloxy) ethoxy] phenyl] -9H-fluorene, 9,9-bis [4- [2-] (Glysidyloxy) ethyl] phenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3-methylphenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3 , 5-Dimethylphenyl] -9H-fluorene, and 9,9-bis (6-glycidyloxynaphthalene-2-yl) -9H-fluorene and other epoxy group-containing fluorene compounds; dimeric acid glycidyl ester, triglycidyl ester, etc. Glycidyl ester type epoxy resin; glycidylamine type epoxy resin such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethaxylylene diamine, and tetraglycidylbisaminomethylcyclohexane; heterocycle such as triglycidyl isocyanurate. Formula epoxy resin; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [ 4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy)) Phenyl] -1- [4- [1- [4- (2,3) -Epoxy propoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetra Tetrafunctional epoxy resins such as glycidoxybiphenyl; 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol can be mentioned. The 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel).

Examples of the oxetane compound that can be suitably used as the polyfunctional crosslinkable compound (D) include bis-1-ethyl-3-oxetanyl methyl ether and 1,4-bis-3-ethyloxetane-3-ylmethoxymethylbenzene. Examples include bifunctional or higher oxetane compounds.

Further, the compound represented by the following formula (d1-6) can be suitably used as the polyfunctional crosslinkable compound (D).

（式（ｄ１−６）中、Ｒ^ｄ２０〜Ｒ^ｄ２２は、直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−ＮＨ−及びこれらの組み合わせからなる基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｅ^１〜Ｅ^３は、エポキシ基、オキセタニル基、エチレン性不飽和基、アルコキシシリル基、イソシアネート基、ブロックイソシアネート基、チオール基、カルボキシ基、水酸基及びコハク酸無水物基からなる群より選択される少なくとも１種の置換基又は水素原子である。ただし、Ｅ^１〜Ｅ^３のうち少なくとも２つは、エポキシ基及びオキセタニル基からなる群より選択される少なくとも１種である。）

(In the formula (d1-6), R ^{d20 to} R ^d22 are linear, branched or cyclic alkylene groups, arylene groups, -O-, -C (= O)-, -NH- and these. It is a group composed of a combination, and may be the same or different from each other. E ^{1 to} E ³ are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate. At least one substituent or hydrogen atom selected from the group consisting of a group, a thiol group, a carboxy group, a hydroxyl group and a succinic anhydride group. However, at least two of ^{E 1 to} E ^{3 are epoxy groups.} And at least one selected from the group consisting of oxetanyl groups.)

In the formula (d1-6) ^{, for example, at least two groups represented by R d20} and E ¹ , R ^d21 and E ² , and R ^d22 and E ³ are each represented by the following formula (d1-6a). It is preferable that each group is a group represented by the following formula (d1-6a). The groups represented by the plurality of formulas (d1-6a) bonded to one compound are preferably the same group.
^{-LC d} (d1-6a)
(In the formula (d1-6a), L is a group consisting of a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (= O)-, -NH- and a combination thereof. C ^d is at least one selected from the group consisting of an epoxy group and an oxetanyl group. In the formula (d1-6a), L and C ^d may be bonded to form a cyclic structure. )

In the formula (d1-6a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is a carbon atom. An arylene group having a number of 5 to 10 is preferable. In the formula (d1-6a), L is a linear group consisting of an alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C (= O)-, -NH-, and a combination thereof. At least one of a linear alkylene group having 1 to 3 carbon atoms and a phenylene group such as a methylene group, or with these, −O−, −C (= O) − and NH− A group consisting of a combination of at least one of the above is preferable.

（式（ｄ１−６ｂ）中、Ｒ^ｄ２３は、水素原子又はメチル基である。） In the formula (d1-6a), when L and C ^d are bonded to form a cyclic structure, for example, a branched alkylene group and an epoxy group are bonded to form a cyclic structure (alicyclic structure). In the case of forming a structure having an epoxy group of (d1-6b), an organic group represented by the following formula (d1-6b) or (d1-6c) can be mentioned.

(In formula (d1-6b), R ^d23 is a hydrogen atom or a methyl group.)

Hereinafter, examples of the compound represented by the formula (d1-6) include an epoxy compound having at least one group selected from the group consisting of an oxylanyl group, an oxetanyl group, and an alicyclic epoxy group. It is not limited to.

Further, examples of the compound that can be suitably used as the polyfunctional crosslinkable compound (D) include a siloxane compound having two or more glycidyl groups in the molecule (hereinafter, also simply referred to as “siloxane compound”).

The siloxane compound is a compound having a siloxane skeleton composed of a siloxane bond (Si—O—Si) and two or more glycidyl groups in the molecule.
Examples of the siloxane skeleton in the siloxane compound include a cyclic siloxane skeleton, a polysiloxane skeleton (for example, linear or branched silicone (linear or branched polysiloxane), and a cage-type or ladder-type polysil. Sesquioxane, etc.) and the like can be mentioned.

As the siloxane compound, a compound having a cyclic siloxane skeleton represented by the following formula (d1-7) (hereinafter, may be referred to as “cyclic siloxane”) is preferable.

Wherein ^{(d1-7), R d24,} and ^{R d25} represents a monovalent group or an alkyl group containing a glycidyl group. However, among the x1 amino ^{R d24} and x1 amino ^{R d25} in the compound represented by formula (d1-7), of at least two is a univalent group containing a glycidyl group. Further, x1 in the equation (d1-7) indicates an integer of 3 or more. Incidentally, ^{R d24, R d25} in the compound represented by formula (d1-7) may be the same or different. Further, the plurality of R ^d24s may be the same or different. The plurality of R ^d25s may be the same or different.

As the monovalent group containing the glycidyl group, ^{a glycidyl ether group represented by −DOR d26} [D represents an alkylene group and R ^d26 represents a glycidyl group] is preferable. Examples of the D (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms such as methylene group, methylmethylene group, dimethylmethylene group, dimethylene group and trimethylene group. be able to.

Examples of the alkyl group include linear chains having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. Alkyl groups in the form of or branched chains can be mentioned.

X1 in the formula (d1-7) represents an integer of 3 or more, and among them, an integer of 3 to 6 is preferable in terms of excellent cross-linking reactivity when forming a cured film.

The number of glycidyl groups contained in the molecule of the siloxane compound is 2 or more, preferably 2 to 6 from the viewpoint of excellent cross-linking reactivity when forming a cured film, and particularly preferably 2 to 4.

In addition to the siloxane compound represented by the formula (d1-7), the photosensitive resin composition includes an alicyclic epoxy group-containing cyclic siloxane and an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169. , And a compound having a siloxane skeleton such as an organopolysilsesquioxane resin having at least two epoxy functional groups may be contained in one molecule described in JP-A-2008-19422.

More specific examples of the siloxane compound include cyclic siloxanes having two or more glycidyl groups in the molecule, which are represented by the following formulas. Examples of the siloxane compound include trade names "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", and "X-40-2740". Commercially available products such as (above, manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

The content of the polyfunctional crosslinkable compound (D) is preferably 1 to 40% by mass, preferably 3 to 30% by mass, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. More preferably. By setting the content of the polyfunctional crosslinkable compound (D) in the above range, it is easy to obtain a photosensitive resin composition capable of forming a cured film that generates less gas.

The ratio of the content [g] of the alkali-soluble resin (A) to the content [g] of the polyfunctional crosslinkable compound (D) in the photosensitive resin composition is in the range of 15: 1 to 0.5: 1. It is preferably in the range of 10: 1 to 1: 1 and even more preferably in the range of 8: 1 to 2: 1. By using the alkali-soluble resin (A) and the polyfunctional crosslinkable compound (D) in a ratio within such a range, it is particularly easy to obtain a photosensitive resin composition capable of forming a cured film that generates less gas.

<Colorant (E)>
The photosensitive resin composition may contain a colorant (E). The colorant (E) is not particularly limited, but for example, a compound classified as Pigment in the Color Index (CI; The Society of Dyers and Colorists), specifically, a compound. It is preferable to use one having a color index (CI) number as shown below.

Examples of preferably usable yellow pigments include C.I. I. Pigment Yellow 1 (hereinafter, "CI 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 preferably usable orange pigments include C.I. I. Pigment Orange 1 (hereinafter, "CI 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 suitably usable purple pigments include C.I. I. Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50. Can be mentioned.

Examples of preferably usable red pigments include C.I. I. Pigment Red 1 (Hereinafter, "CI 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 preferably usable blue pigments include C.I. I. Pigment Blue 1 (hereinafter, "CI 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 the above other hues that can be suitably 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. Examples thereof include black pigments such as Pigment Black 7.

Further, the photosensitive resin composition may contain a light-shielding agent as the colorant (E). The photosensitive resin composition containing a light-shielding agent is suitably used for forming a black matrix or a black column spacer in a liquid crystal display panel, or forming a bank for partitioning a light emitting layer in an organic EL element.
As described above, the cured film formed by using the photosensitive resin composition generates less gas. Therefore, the bank formed by using the photosensitive resin composition is less likely to damage the organic light emitting material (light emitting layer) and the electrode in the organic EL element. When the bank contains a light-shielding agent, it is easy to prevent internal reflection in the organic EL element and unnecessary light entering the organic EL element.
From the above, the photosensitive resin composition containing a light-shielding agent is particularly preferably used for forming a bank for partitioning a light emitting layer in an organic EL element.

When the colorant (E) is used as a light-shielding agent, it is preferable to use a black pigment or a purple pigment as the light-shielding agent. Examples of black pigments and purple pigments include carbon blacks, perylene pigments, lactam pigments, titanium blacks, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides and composite oxides. , Metal sulfides, metal sulfates, metal carbonates, and other pigments, regardless of whether they are organic or inorganic.

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

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

Among the carbon blacks that have been subjected to the treatment for introducing the acidic groups described above, carboxylic acid groups and carboxylic acids are used from the viewpoint of achieving high resistance of the light-shielding cured film formed by using the photosensitive resin composition. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid base is preferable.

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

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

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of acidic groups introduced into carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol, based on 100 g of carbon black.

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

Further, a perylene-based pigment is also preferable as the light-shielding agent. 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). Perylene-based pigments can be mentioned. As commercial products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene-based pigments.

式（ｅ−１）中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^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, and R ^e3 and R ^e4 independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a hydrogen atom, respectively. 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１〜７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１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^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 independently alkyl groups having a hydrogen atom and 1 to 22 carbon atoms, and may contain heteroatoms of N, O, S, or P, respectively. Good. 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, for example, JP-A-62-1753. , No. 63-26784 can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

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

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

In formula (e-4), X ^e shows a double bond and is an E-form or a Z-form independently as geometric isomers, and ^Re9 is independently a hydrogen atom, a methyl group, a nitro group, and a methoxy. ^{Represents a} group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, Re 10 independently represents a hydrogen atom, a methyl group, or a phenyl group, and ^{Re 11} independently represents a hydrogen atom. , Methyl group, or chlorine atom.
The compound represented by the 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 dihydroindron ring because the compound represented by the formula (e-4) can be easily produced, and ^Re11 is bonded to the 4-position of the dihydroindron ring. It is preferable to do so. From the same ^viewpoint, R ^{e9, R e10,} and ^{R e11} are preferably hydrogen atom.
The compound represented by the formula (e-4) has an EE form, a ZZ form, and an EZ form as geometric isomers, but may be a single compound of any one of these, or these geometric isomers. May be a mixture of.
The compound represented by the formula (e-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

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

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

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

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

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

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

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

Further dispersants may be used to uniformly disperse the colorants in the 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, it is preferable to use an acrylic resin-based dispersant as the dispersant.
In addition, gas may be generated from the cured film due to the dispersant. Therefore, it is also preferable that the colorant is dispersed without using a dispersant.

Further, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when they are used in combination, 10 to 80 parts by mass of the organic pigment is used with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferable to use it in the range of 20 to 40 parts by mass, and it is more preferable to use it in the range of 20 to 40 parts by mass.

In the photosensitive resin composition, a dye can be used as the colorant (E) in addition to the pigment. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the photosensitive resin composition of the present embodiment include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, and methine dyes. Examples include phthalocyanine dyes.
Further, these dyes can be raked (chlorinated) to be dispersed in an organic solvent or the like, and this can be used as a 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 dyes and the like described can also be preferably used.
These dyes can also be used in combination with the above-mentioned pigments (for example, perylene-based pigments, lactam-based pigments, AgSn alloy fine particles, etc.).

The amount of the colorant (E) used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and typically, the photosensitive resin composition excluding the mass of the organic solvent (S) described later. It is preferably 5 to 70% by mass, more preferably 25 to 60% by mass, based on the mass of the product.

The colorant (E) is preferably added to the photosensitive resin composition after being prepared as a dispersion liquid dispersed in the presence or absence of the dispersant at an appropriate concentration.
In this specification, the amount of the above-mentioned colorant (E) used can be defined as a value including the existing dispersant.

<Fluorine resin (F)>
The photosensitive resin composition may contain a fluororesin (F) (hereinafter, also referred to as “component (F)”). When the photosensitive resin composition contains the fluororesin (F), liquid repellency is imparted to the cured film formed by using the photosensitive resin composition.
For example, when a light emitting layer is formed in a region partitioned by a bank by a printing method such as an inkjet method on a substrate for an organic EL element having a bank formed by using a photosensitive resin composition, the bank By repelling the ink, it is possible to prevent the ink from adhering to the bank and the ink from being mixed with the adjacent pixels when the ink is injected into the area surrounded by the bank.

The fluorine-based resin (F) is not particularly limited as long as it is a resin containing fluorine atoms and can impart liquid repellency to the cured film formed by using the photosensitive resin composition. The fluorine-based resin (F) may be a homopolymer of a monomer containing a fluorine atom, or a copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom.

Preferable examples of the fluororesin (F) include a copolymer obtained by at least copolymerizing (f1) a monomer having an ethylenically unsaturated group and a fluorine atom with (f2) (meth) acrylic acid. .. When such a fluororesin (F) is used, it is easy to use the photosensitive resin composition to form a cured film having excellent liquid repellency, particularly a bank for an organic EL element having excellent liquid repellency.

((F1) Monomer having an ethylenically unsaturated group and a fluorine atom)
The monomer having an ethylenically unsaturated group and a fluorine atom (hereinafter, also referred to as “(f1) monomer”) is not particularly limited as long as it has an ethylenically unsaturated group and a fluorine atom. Examples of such a (f1) monomer include compounds represented by the following formula (f1-1). These (f1) monomers can be used alone or in combination of two or more.

In formula (f1-1), X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom, a methyl group, or a perfluoromethyl group, and X ⁴ and X ⁵ Indicates a hydrogen atom, a fluorine atom, or a perfluoromethyl group. Rf represents a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms, a represents an integer of 0 to 3, and b and c are independently 0. Or 1 is indicated. When Rf is a fluorine-containing alkyl group, the number of carbon atoms is preferably 2 to 20, more preferably 3 to 10, and particularly preferably 4 to 6. When Rf is a fluorine-containing alkyl group having an ether bond, the number of carbon atoms is preferably 2 to 50, more preferably 3 to 20, and particularly preferably 4 to 6.

The content of the unit derived from the (f1) monomer is preferably 30 to 80% by mass, more preferably 40 to 60% by mass, based on the mass of the fluororesin (F). When the content of the unit derived from the (f1) monomer in the fluororesin (F) is within the above range, the photosensitive resin composition can easily form a cured film having excellent liquid repellency, and the photosensitive resin composition The compatibility between the fluororesin (F) and other components in the above tends to be good.

Further, the (f1) monomer _{preferably has a group represented by − (CF 2} ) _t F (t = 1 to 10). t is more preferably 1 to 8, and even more preferably 2 to 6. (F1) When the monomer has the above group, it is easy to form a cured film having excellent liquid repellency due to the photosensitive resin composition.

<(F2) (meth) acrylic acid>
The fluororesin (F) preferably contains a unit derived from (f2) (meth) acrylic acid, which is a monomer having a carboxyl group, in order to improve the developability of the photosensitive resin composition.

The content of the unit derived from (f2) (meth) acrylic acid is preferably 0.1 to 20% by mass with respect to the mass of the fluororesin (F). When the content of the unit derived from (f2) (meth) acrylic acid in the fluororesin (F) is within the above range, a photosensitive resin capable of forming a cured film having good developability and excellent liquid repellency. Easy to obtain composition.

If necessary, the fluororesin (F) may be copolymerized with a monomer other than the above-mentioned (f1) monomer and (f2) monomer. Examples of such other monomers include various monomers described below.

((F3) Monomer having an ethylenically unsaturated group and an epoxy group)
The fluororesin (F) is preferably a copolymer obtained by further copolymerizing a monomer having an ethylenically unsaturated group and an epoxy group (hereinafter, also referred to as “(f3) monomer”). By copolymerizing the (f3) monomer, the liquid repellency of the cured film formed by the photosensitive resin composition can be further improved.

As the (f3) monomer, glycidyl (meth) acrylate, an alicyclic epoxy compound represented by the following formulas (f3-1) to (f3-3), a carboxyl group of (meth) acrylic acid and a bifunctional or higher epoxy. Monomers obtained by reacting with the epoxy groups of compounds, monomers obtained by reacting the hydroxyl groups or carboxyl groups of acrylic monomers having hydroxyl groups or carboxyl groups in the side chains with the epoxy groups of bifunctional or higher epoxy compounds, etc. Can be mentioned. Of these, glycidyl (meth) acrylate is preferable. These (f3) monomers can be used alone or in combination of two or more.

In the formulas (f3-1), (f3-2), and (f3-3), R ^f0 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^f1 represents a hydrogen atom or a methyl group. u represents an integer of 1 to 10, and v and w each independently represent an integer of 1 to 3.

When the fluororesin (F) contains a unit derived from the (f3) monomer, the content of the unit in the fluororesin (F) is 1 to 40% by mass with respect to the mass of the fluororesin (F). Is preferable, and 5 to 15% by mass is more preferable. When the content of the unit derived from the (f3) monomer in the fluororesin (F) is within the above range, it is easy to obtain a photosensitive resin composition capable of forming a cured film having good liquid repellency.

(Monomer having a structure represented by the formula (f4) (f4-1))
The fluororesin (F) is further copolymerized with an ethylenically unsaturated group and a monomer having a structure represented by the following formula (f4-1) (hereinafter, also referred to as “(f4) monomer”). It is preferably a polymer. By copolymerizing the (f4) monomer, it is easy to obtain a photosensitive resin composition having excellent developability, and the compatibility between the fluororesin (F) and other components in the photosensitive resin composition can be improved. ..

The monomer (f4) more preferably has an ethylenically unsaturated group and a structure represented by the following formula (f4-2).

In the formulas (f4-1) and (f4-2), R ^f2 represents an alkylene group having 1 to 5 carbon atoms, and may be linear or branched. Among them, an alkylene group having 1 to 3 carbon atoms is preferable, and an ethylene group is most preferable. R ^f3 represents an alkyl group having 1 to 20 carbon atoms which may have a hydrogen atom, a hydroxyl group, or a substituent, and may be linear or branched. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is most preferable. Examples of the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. x indicates an integer of 1 or more, preferably an integer of 1 to 60, and more preferably an integer of 1 to 12.

Examples of such a (f4) monomer include compounds represented by the following formula (f4-3). These (f4) monomers can be used alone or in combination of two or more.

In formula (f4-3), R ^f4 represents a hydrogen atom or a methyl group. R ^f2 , R ^f3 , and x are synonymous with the above formulas (f4-1) and (f4-2).

The content of the unit derived from the (f4) monomer is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, based on the mass of the fluororesin (F). Within the above range, the developability of the photosensitive resin composition and the compatibility between the fluororesin (F) and other components in the photosensitive resin composition tend to be good, which is preferable.

((F5) Monomer having a silicon atom)
The fluororesin (F) is preferably a copolymer obtained by further copolymerizing a monomer having a silicon atom (hereinafter, also referred to as “(f5) monomer”). The (f5) 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 this (f5) monomer, the liquid repellency of the cured film formed by the photosensitive resin composition can be further improved.

Examples of such a (f5) monomer include compounds represented by the following formula (f5-1). These (f5) monomers can be used alone or in combination of two or more.

In the formula (f5-1), R ^f5 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom or a methyl group. R ^f6 represents an alkylene group having 1 to 20 carbon atoms or a phenylene group, and is preferably an alkylene group having 1 to 10 carbon atoms. R ^f7 and R ^f8 independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and are preferably an alkyl group having 1 to 3 carbon atoms. When multiple R ^f7 is bonded to Si, R ^f7 the plurality of may be the same or different. Also, if a plurality of Si is ^{(OR f8)} are attached, the plurality of ^{(OR f8)} may or may not be the same. p is 0 or 1, preferably 1. q is an integer of 1-3, preferably 2 or 3, and more preferably 3.

The content of the unit derived from the (f5) monomer is preferably 20% by mass or less, more preferably 10% by mass or less, based on the mass of the fluororesin (F). Within the above range, the liquid repellency and compatibility with other components of the photosensitive resin composition tend to be good, which is preferable.

As the other monomer of the above-mentioned monomer, various monomers having an ethylenically unsaturated group can be used, and among them, an acrylic monomer is preferable. Preferable examples of the acrylic monomer include 2-hydroxyethyl methacrylate (HEMA), N-hydroxymethylacrylamide (N-MAA), methyl methacrylate (MAA), cyclohexyl methacrylate (CHMA), isobonyl methacrylate (IBMA) and the like. Can be mentioned. The content of the unit derived from these other monomers in the fluororesin (F) is preferably 0 to 25% by mass with respect to the mass of the fluororesin (F).

A known method can be used as a method for obtaining a copolymer by reacting the (f1) monomer, the (f2) monomer, and other monomers if necessary.

The mass average molecular weight of the fluororesin (F) is preferably 2000 to 50000, and more preferably 5000 to 20000. By setting the mass average molecular weight of the fluororesin (F) to 2000 or more, the heat resistance and strength of the cured film formed by the photosensitive resin composition can be improved, and by setting it to 50,000 or less, the photosensitive film is photosensitive. The developability of the resin composition can be improved.

The content of the fluororesin (F) in the photosensitive resin composition is 0.1 to 10% by mass with respect to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. Is preferable, and 0.2 to 5% by mass is more preferable. When the photosensitive resin composition contains the fluororesin (F) in such an amount, the photosensitive resin composition is used while making the photosensitive resin composition excellent in sensitivity, developability, and resolution. It is easy to impart good liquid repellency to the cured film formed in the above process.

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

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

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

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

<Other ingredients>
The photosensitive resin composition may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, an antifoaming agent, and a silane coupling agent, if necessary. As any of the additives, conventionally known ones can be used.
The photosensitive resin composition preferably contains a silane coupling agent because it has a good shape and easily forms a cured film having excellent adhesion to a substrate. As the silane coupling agent, conventionally known ones can be used without particular limitation.
Examples of the surfactant include anionic, cationic and nonionic compounds, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine. Examples include compounds.

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

<< A bank for partitioning a cured film and a light emitting layer in an organic EL element, a substrate for an organic EL element having a bank, and an organic EL element having a bank >>
A cured film is formed by curing the thin film formed by using the photosensitive resin composition described above by exposure and heating.
Applications of the cured film include an insulating film. When the photosensitive resin composition does not contain the colorant (E), a transparent insulating film is formed. When the photosensitive resin composition contains the colorant (E), a colored insulating film is formed. In particular, when the colorant (E) is a light-shielding agent, a light-shielding insulating film is formed.
Preferable examples of the light-shielding black insulating film include a black partition wall in a black matrix and a black column spacer provided in panels for various image display devices.
When the photosensitive resin composition contains a chromatic colorant (E) such as RGB, a colored cured film can be formed in a region partitioned by a black matrix to produce a color filter.
For example, the above-mentioned black matrix and a color filter containing a chromatic cured film as a cured product are suitably used in various display devices.

Further, as described above, less gas is generated from the cured film. Therefore, the cured film formed by using the photosensitive resin composition is suitably used as a bank for partitioning the light emitting layer in the organic EL element.
The bank is formed on a substrate for an organic EL element so as to be in contact with an electrode layer such as ITO and a light emitting layer made of an organic light emitting material. Pixels are formed by partitioning the light emitting layer by banks. Here, when the electrode layer and the light emitting layer are contaminated with gas containing various components generated from the bank, deterioration is promoted.
However, when the cured film formed by using the photosensitive resin composition described above is applied as a bank, the generation of gas from the bank is suppressed, so that the electrode layer and the light emitting layer are less likely to deteriorate, and the organic EL element Durability is improved. That is, the organic EL device including the cured film formed by using the photosensitive resin composition described above as a bank has excellent durability.

Further, a substrate having a bank formed by using the photosensitive resin composition described above is useful as a substrate for an organic EL element. By using such a substrate for an organic EL element, it is possible to manufacture an organic EL element having excellent durability in which deterioration of the electrode layer and the light emitting layer is suppressed.

≪Manufacturing method of cured film≫
As a method for producing a cured film, a photopolymerizable monomer (B) is polymerized in a thin film of a photosensitive resin composition, and a cross-linking reaction between an alkali-soluble resin (A) and a polyfunctional cross-linking compound (D) is performed. The method is not particularly limited as long as it is a method capable of forming a cured film by producing.

In order to polymerize the photopolymerizable monomer (B), exposure is usually performed. Further, in order to cause a cross-linking reaction between the alkali-soluble resin (A) and the polyfunctional cross-linking compound (D), the thin film of the exposed or unexposed photosensitive resin composition is heated.

A suitable method for producing the cured film is
The process of forming a coating film by applying the photosensitive resin composition and
The process of exposing the coating film and
Examples thereof include a step of curing the exposed coating film and a method including.

In order to form a cured film using the photosensitive resin composition, the photosensitive resin composition is applied onto a substrate selected according to the application of the cured film to form a coating film. The method for forming the coating film is not particularly limited, but for example, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used. It is said.

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

Next, the coating film is exposed. The exposure is performed by irradiating with active energy rays such as ultraviolet rays and excimer laser light. The exposure may be regioselective, for example, by a method of performing exposure through a negative mask. The energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably about ^{40 to 200 mJ / cm 2, for example.}

When the coating film is exposed in a regioselective manner, the exposed film is patterned with a developing solution to form a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer is appropriately selected according to the composition of the photosensitive resin composition. As the developing solution, for example, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt can be used.

The exposed coating film or the developed patterned coating film is then cured to form a cured film. Such curing causes a cross-linking reaction between the alkali-soluble resin (A) and the polyfunctional cross-linking compound (D). Therefore, in order to perform curing, baking is performed on the exposed coating film or the patterned coating film after development.
The baking temperature is not particularly limited as long as the curing proceeds well, but is preferably 180 to 280 ° C, more preferably 190 to 260 ° C.
By baking as described above, a cured film of the photosensitive resin composition can be obtained.

<< Method of manufacturing a bank for partitioning the light emitting layer in an organic EL element >>
The method for producing a bank for partitioning the light emitting layer in the organic EL element is not particularly limited as long as the bank can be produced at a predetermined position on the substrate for the organic EL element.
The preferred method is
A process of forming a coating film on a substrate for an organic EL element by applying a photosensitive resin composition, and
A process of regioselectively exposing a portion of the coating film corresponding to the position of the bank,
The process of developing the exposed coating film and
Examples thereof include a step of curing the developed coating film and a method including.

A typical example of a substrate is a transparent substrate having a transparent electrode layer (anode) made of ITO or the like at a portion corresponding to a portion where a light emitting layer is formed on one of the main surfaces.
The bank is formed so as to surround the region where the light emitting layer is formed while being in contact with the end portion of the transparent electrode layer.

A method of applying a photosensitive resin composition to a substrate for an organic EL element, a method of position-selectively exposing a portion corresponding to the position of a bank in the coating film, a method of developing the exposed coating film, and a method of developing the exposed coating film. The method for curing the developed coating film is the same as the method described above for the method for producing the cured film.

By the method described above, a substrate having a bank for partitioning the light emitting layer can be obtained at a predetermined position on the substrate for the organic EL element.

≪Manufacturing method of organic EL element≫
The organic EL element is manufactured by using the substrate for the organic EL element provided with the bank described above.
The method includes a step of forming a light emitting layer in a region partitioned by a bank in a substrate for an organic EL element.
In the substrate for an organic EL element provided with a bank, a transparent electrode layer (anode) made of ITO or the like is exposed in a region partitioned by the bank.
In a typical method, a hole transport layer is laminated on the electrode layer (anode). Then, the electron transport layer and the electrode layer (cathode) are laminated on the hole transport layer in this order, and an organic EL element is manufactured. If necessary, a TFT, a color filter, or the like is further combined as appropriate.
The method of forming the hole transport layer, the light emitting layer, the electron transport layer and the like in the region partitioned by the bank is not particularly limited, and may be a vapor deposition method or a printing method. The printing method is preferable, and the inkjet method is particularly preferable as the printing method because the loss of the material for layer formation is small and it is easy to quickly form a layer having a desired film thickness at a predetermined position.

Since the organic EL element manufactured by the above method includes a bank that generates less gas, deterioration of the electrode layer and the light emitting layer is suppressed, and the durability is excellent.

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

[Preparation Example 1]
In a 1500 mL four-necked flask, 275 g (0.5 mol, epoxy equivalent 292) of an epoxy compound represented by the following formula, 100 mg of 2,6-di-tertbutyl-4-methylphenol and 72 g of acrylic acid are placed together with a catalyst. It was charged and melted by heating at 90 to 100 ° C. while blowing air into it at a rate of 25 mL / min.

Next, the temperature was gradually raised while the solution was cloudy, and the solution was heated to 120 ° C. to completely dissolve it. Here, the solution gradually became transparent and viscous, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. Then, it was cooled to room temperature to obtain a colorless transparent solid bisphenol fluorene type epoxy acrylate having the following structure.

Next, 650 g of propylene glycol monomethyl ether acetate was added to 347.4 g (0.5 mol) of the above-mentioned bisphenol fluorene type epoxy acrylate thus obtained and dissolved, and then the compound of the following formula (b1) -1 (hereinafter referred to as the compound). , Also referred to as compound (b1) -1,) (0.25 mol), was mixed with the catalyst, gradually heated and reacted at 130 ° C. for 4 hours.
Compound (b1) -1 is a tetracarboxylic dianhydride represented by the following formula (norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'. ', 6, 6''-tetracarboxylic dianhydride).

After confirming the disappearance of the acid anhydride group, 30 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a bisphenol fluorene type epoxy acrylate and an acid anhydride (compound (b1). ) -1) and resin A1 which is a cardo resin produced from the above were obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

[Preparation Example 2]
Resin A2, which is a cardo resin, was obtained in the same manner as in Preparation Example 1 except that the reaction using 30 g of 1,2,3,6-tetrahydrophthalic anhydride was not carried out.

[Preparation Example 3]
Resin A3, which is a cardo resin, was used in the same manner as in Example 1 except that 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used in equimolar amounts instead of compound (b1) -1. Obtained.

[Preparation Example 4]
Resin A4, which is a cardo resin, was obtained in the same manner as in Preparation Example 3 except that the reaction using 30 g of 1,2,3,6-tetrahydrophthalic anhydride was not carried out.

[Preparation Example 5]
Resin A5, which is a cardo resin, was obtained in the same manner as in Preparation Example 1 except that the amount of 1,2,3,6-tetrahydrophthalic anhydride added was changed to 15 g with respect to Preparation Example 1.

[Examples 1 to 10, Comparative Example 1, and Comparative Example 2]
In Examples and Comparative Examples, the resins A1 to A5 obtained in Preparation Examples 1 to 5 and the resins A6 having the following structure were used as the alkali-soluble resins (A) (component (A)). The numerical value at the lower right of the parentheses in the following formula is the ratio (mass%) of each structural unit in the resin A6.

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

In Examples and Comparative Examples, a compound having the following structure was used as the photopolymerization initiator (C) (component (C)).

In Examples and Comparative Examples, the following D1, D2, and D4 as the polyfunctional crosslinkable compound (D) and the siloxane-based polyfunctional epoxy compound D3 (molecular weight: 3400, epoxy equivalent: 147 g / eq) in one molecule. The number of epoxy groups: about 23) was used.
The molecular weight of D1 is 737.27, and the epoxy equivalent is 184 g / eq. The number of epoxy groups in one molecule is 4.
The molecular weight of D2 is 381.42, and the epoxy equivalent is 127 g / eq. The number of epoxy groups in one molecule is 3.
The molecular weight of D4 is 252.31, and the epoxy equivalent is 126 g / eq. The number of epoxy groups in one molecule is 2.

In Examples and Comparative Examples, the following E1 to E3, which are light-shielding agents, were used as the colorants (E) (component (E)).
E1: Lactam pigment E2: Perylene pigment E3: AgSn pigment

Table 1, the type and amount of (A) component, (B) component 7 parts by mass, (C) component 8 parts by mass, and the type and amount of (D) component 10 parts by mass shown in Table 1. 45 parts by mass of the component (E) of the type described in 1 is uniformly mixed in the organic solvent so that the mass ratio of the components other than the organic solvent is 20% by mass, and the photosensitivity of each Example and Comparative Example is obtained. A sex resin composition was obtained.
In Comparative Example 1, 40 parts by mass of the component (A) was used without using the polyfunctional crosslinkable compound (D).
As the organic solvent, a mixed solvent consisting of 60% by mass of propylene glycol monomethyl ether acetate, 20% by mass of 3-methoxybutyl acetate, and 20% by mass of N, N, N', N'-tetramethylurea is used. There was.

<Gas generation evaluation>
The photosensitive resin compositions of Examples and Comparative Examples were applied onto a 10 cm × 10 cm glass substrate, and then dried at 100 ° C. for 120 seconds to form a coating film.
Next, the entire surface was exposed at ^{an exposure amount of 50 mJ / cm 2} using an exposure machine using a high-pressure mercury lamp for the coating film.
The exposed coating film was post-baked at 230 ° C. for 30 minutes to obtain a cured film having a film thickness of 2 μm.

Using the formed cured film as a sample, the amount of generated gas was evaluated by gas chromatography-mass spectrometry (P & T-GC / MS) equipped with a purge & trap sampler (heat desorption device). The measurement and the quantification of gas were carried out according to the procedures (i) to (iii) below.
(I) Gas generation and collection in the secondary adsorption tube Put 1 mg of the cured film in the primary trap tube and heat it at 230 ° C. for 10 minutes using a heat desorption device (manufactured by PerkinElmer: Tarbo Matrix ATD) to desorb. The gas was adsorbed on the secondary trap tube.
(Ii) GC / MS analysis The secondary trap tube was heated at 250 ° C. for 1 minute, and the desorbed gas was analyzed by GC / MS (manufactured by Agilent Technologies: 7890B (GC), 5977AMSD (MS)).
(Iii) Quantitative analysis Quantitative analysis was performed from each peak area of the chart obtained by PT-GC / MS analysis of the resin composition. Specifically, the total area% of the detected outgas peaks was set as the evaluation value.

Based on the obtained evaluation value (total area%), the amount of generated gas was evaluated according to the following criteria. If the evaluation is 3 to 5, it is understood that the amount of gas generated is small. The evaluation results are shown in Table 1.
5: less than the value of the evaluation value is 1.0E ^8.
4: less than the value of the evaluation value is 1.0E ⁸ more than 2.5E ^8.
3: The evaluation value is 2.5E ⁸ or more and less ^{than 5.0E 8.}
2: The evaluation value is 5.0E ⁸ or more and less ^{than 1.0E 9.}
1: The evaluation value is 1.0E ⁹ or more.

According to the examples, the alkali-soluble resin (A), the photopolymerizable monomer (B), the photopolymerization initiator (C), and the polyfunctional crosslinkable compound (D) are contained, and the alkali-soluble resin (A) is contained. However, it can be seen that the cured film formed by using the photosensitive resin composition containing the cardo resin and having an epoxy equivalent of the polyfunctional crosslinkable compound (D) of 50 to 350 g / eq has a small amount of gas generated. ..
According to the comparative example, when the photosensitive resin composition does not contain the polyfunctional crosslinkable compound (D), or when the photosensitive resin composition contains an acrylic resin as the alkali-soluble resin (A) instead of the cardo resin. It can be seen that the amount of gas generated from the cured film formed by using the photosensitive resin composition is large.

Claims (15)

An alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a polyfunctional crosslinkable compound (D) having a plurality of epoxy groups or oxetanyl groups in one molecule. Including
The alkali-soluble resin (A) contains a resin having a cardo skeleton, and the alkali-soluble resin (A) contains a resin.
Wherein an epoxy equivalent or oxetanyl equivalent 50 to 350 g / eq polyfunctional crosslinking compounds (D), see containing the polyfunctional crosslinkable compound (D) is a siloxane compound having three or more epoxy groups in the molecule, The ratio of the content [g] of the alkali-soluble resin (A) to the content [g] of the polyfunctional crosslinkable compound (D) is in the range of 15: 1 to 0.5: 1, and is photosensitive. Resin composition. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C) is an oxime ester compound having a fluorene structure. The photosensitive resin composition according to claim 1 or 2, wherein the polyfunctional crosslinkable compound (D) has an epoxy equivalent of 50 to 350 g / eq. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a light-shielding agent as a colorant (E). The resin having the cardo skeleton is the following formula (a-1):

(In the formula (a-1), ^Xa is the following formula (a-2):

In the above formula (a-2), ^Ra1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and ^Ra2 is independent of each other. represent a hydrogen atom or a methyl ^{group, R a3} each independently represent an alkylene group of straight or branched chain, m2 represents 0 or 1, ^{W a} is the following formula (a3):

The ring A in the above formula (a-3) represents an aliphatic ring in which the aromatic ring may be condensed or may have a substituent, and R ^a0 is a hydrogen atom. or a group represented by ^{-CO-Y a} -COOH, Y a represents a divalent residue obtained by removing the acid anhydride group from a dicarboxylic acid anhydride, ^{Z a} is tetracarboxylic dianhydride The tetravalent residue obtained by removing the two acid anhydride groups from the above is shown. Further, in the equation (a-1), m1 represents an integer of 0 to 20. )
The photosensitive resin composition according to any one of claims 1 to 4, which is a resin represented by. The tetracarboxylic dianhydride is based on the following formula (a-4):

(In the formula (a-4), R ^a4 , R ^a5 , and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. , M3 indicates an integer from 0 to 12.)
The photosensitive resin composition according to claim 5, which is a compound represented by. The photosensitive resin composition according to any one of claims 1 to 6 , which is used for forming a bank for partitioning a light emitting layer in an organic EL device. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6. A bank for partitioning a light emitting layer in an organic EL device, which is obtained by curing the photosensitive resin composition according to claim 7. A substrate for an organic EL element, comprising the bank according to claim 9. An organic EL device including the bank according to claim 9. A step of forming a coating film by applying the photosensitive resin composition according to any one of claims 1 to 6.
The step of exposing the coating film and
A method for producing a cured film, which comprises a step of curing the exposed coating film. In the step of exposure, the coating film is regioselectively exposed.
The method for producing a cured film according to claim 12 , further comprising a step of developing the exposed coating film between the step of exposing and the step of curing. A method of manufacturing a bank for partitioning a light emitting layer in an organic EL element on a substrate.
A step of forming a coating film on the substrate by applying the photosensitive resin composition according to claim 7.
A step of regioselectively exposing a portion of the coating film corresponding to the position of the bank,
The process of developing the exposed coating film and
A method comprising a step of curing the developed coating film. The method for manufacturing an organic EL element, which comprises the step of forming a light emitting layer in the region partitioned by the bank in the substrate for the organic EL element according to claim 10.