KR102422588B1 - Photosensitive Resin Composition, Cured Film, Bank for Partitioning Light Emitting Layer of Organic EL Element, Substrate for Organic EL Element, Organic EL Element, Manufacturing Method of Cured Film, Manufacturing Method of Bank, and Manufacturing Method of Organic EL Element - Google Patents

Abstract

A photosensitive resin composition capable of forming a cured film with a small amount of generated gas, a bank for partitioning a light emitting layer in an organic EL device and a cured film formed using the above-described photosensitive resin composition, and an organic EL device having the above bank A method for manufacturing a bank for partitioning a substrate and an organic EL device, a cured film using the above-described photosensitive resin composition and a light emitting layer in an organic EL device, and an organic EL device using the substrate for an organic EL device having the above-mentioned bank A manufacturing method is provided.
A photosensitive resin comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a polyfunctional crosslinkable compound (D) having a plurality of epoxy groups or oxetanyl groups in one molecule Composition WHEREIN: The resin which has a cardo skeleton is made to contain alkali-soluble resin (A), and the compound whose epoxy equivalent or oxetanyl equivalent is 50-350 g/eq is used as a polyfunctional crosslinking|crosslinked compound (D).

Description

BACKGROUND ART A photosensitive resin composition, a cured film, a bank for partitioning a light emitting layer in an organic EL device, a substrate for an organic EL device, an organic EL device, a method for manufacturing a cured film, a method for manufacturing a bank, and a method for manufacturing an organic EL device TECHNICAL FIELD , Cured Film, Bank for Partitioning Light Emitting Layer of Organic EL Element, Substrate for Organic EL Element, Organic EL Element, Manufacturing Method of Cured Film, Manufacturing Method of Bank, and Manufacturing Method of Organic EL Element}

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

Conventionally, optical devices such as organic EL display devices, color filters, and organic TFT arrays are manufactured by forming banks (partition walls) surrounding pixels on a substrate and then providing various functional layers in the area surrounded by the banks. is becoming As a method of easily forming such a bank, a method of forming a bank by a photolithography method using a photosensitive resin composition is known (see Patent Document 1 and Patent Document 2).

Publication No. 2009-204805 International Publication No. 2013/069789 pamphlet

However, when forming a cured film that can be used as a bank according to the method described in Patent Documents 1 and 2, there is a concern that the amount of gas generated from the cured film increases. In the organic EL device, the bank is provided so as to be in contact with an electrode layer such as ITO or a light emitting layer. In addition, when the electrode layer or the light emitting layer is contaminated by the gas generated from the bank, there is a concern that deterioration thereof is accelerated.

Therefore, the photosensitive resin composition which can form the cured film with little amount of generated gas is calculated|required.

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

The present inventors, an alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a polyfunctional crosslinkable compound (D) having a plurality of epoxy groups or oxetanyl groups in one molecule The photosensitive resin composition comprising WHEREIN: A resin which has a cardo backbone is contained in alkali-soluble resin (A), and the epoxy equivalent or oxetanyl equivalent of a polyfunctional crosslinkable compound (D) is 50-350 g/eq. By using , it was found that the above problems could be solved, and the present invention was completed. Specifically, the present invention provides the following.

A 1st aspect of this invention is a polyfunctional crosslinking|crosslinked compound provided with alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a plurality of epoxy groups or oxetanyl groups in one molecule. (D), wherein the alkali-soluble resin (A) contains a resin having a cardo skeleton, and the epoxy equivalent or oxetanyl equivalent of the polyfunctional crosslinkable compound (D) is 50 to 350 g/eq, photosensitive a resin composition.

A second aspect of the present invention is a cured film formed 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, for partitioning of a light emitting layer in an organic EL device, which is formed by curing the photosensitive resin composition used for forming a bank for partitioning a light emitting layer in an organic EL device. is the bank of

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 comprises a step of forming a coating film by applying the photosensitive resin composition according to the first aspect;

exposing the coating film; and

It is a manufacturing method of a cured film including the process of hardening the exposed coating film.

A seventh aspect of the present invention is a method for manufacturing a bank for partitioning a light emitting layer in an organic EL device on a substrate, and as the photosensitive resin composition according to the first aspect, formation of a bank for partitioning a light emitting layer of an organic EL device The process of forming a coating film on a board|substrate by apply|coating the photosensitive resin composition used for, and

A step of positionally exposing a position corresponding to the position of the bank in the coating film;

a process of developing the exposed coating film; and

It is a method including the process of hardening the developed coating film.

An eighth aspect of the present invention is a method for manufacturing an organic EL element, comprising the step of forming a light emitting layer in a region partitioned by banks in a substrate for an 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 bank for partitioning a light emitting layer in an organic EL device and a cured film formed using the aforementioned photosensitive resin composition, and an organic comprising the above bank A substrate for an EL element and an organic EL element, a cured film using the above-mentioned photosensitive resin composition, and a method for manufacturing a bank for partitioning a light emitting layer in an organic EL element, and an organic EL using the substrate for an organic EL element having the above-mentioned bank A method for manufacturing a device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on preferable embodiment.

In addition, in this specification, "~" indicates from above (lower limit) to below (upper limit) unless otherwise specified.

«Photosensitive resin composition»

The photosensitive resin composition is an alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a polyfunctional crosslinkable compound (D) having a plurality of epoxy groups or oxetanyl groups in one molecule includes

Alkali-soluble resin (A) contains resin which has cardo frame|skeleton.

The epoxy equivalent or oxetanyl equivalent of the polyfunctional crosslinkable compound (D) is 50 to 350 g/eq.

The photosensitive resin composition provided with said structure can form the cured film by which gas generation was suppressed.

Hereinafter, essential or optional 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 alkali-soluble resin (A) (it also describes as "(A) component" in this specification). Alkali-soluble resin (A) contains resin (Hereinafter, it also describes as "(A1) cardo resin") which has (A1) cardo structure.

In addition, in this specification, alkali-soluble resin (A) refers to resin provided with the functional group (For example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) which makes it alkali-soluble in a molecule|numerator.

Although it is not certain about the point which the photosensitive resin composition of this embodiment can form the cured film by which gas generation was suppressed, it is thought that there exist the following influences.

That is, first, (A1) cardo resin has bulkiness of cardo structure.

On the other hand, in forming a cured film using the photosensitive resin composition, bridge|crosslinking generate|occur|produces between (A1) cardo resin and the polyfunctional crosslinkable compound (D) provided with a some epoxy group or oxetanyl group in 1 molecule.

These influences are compatible with each other, so that when forming a cured film using the photosensitive resin composition, when processing a laminate structure having a cured film of the photosensitive resin composition to form various elements, and when forming a cured film of the photosensitive resin composition It is considered that generation|occurrence|production of gas from a cured film when using branch elements etc. is suppressed.

(A1) Resin which has cardo frame|skeleton will not be specifically limited if it is resin which has predetermined alkali solubility. The cardo skeleton refers to a skeleton in which the second cyclic structure and the third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. In addition, the 2nd cyclic structure and the 3rd cyclic structure may be the same structure or different structures may be sufficient as them.

A typical example of the cardo skeleton is a skeleton in which two aromatic rings (eg, benzene rings) are bonded to the carbon atom at the 9th position of the fluorene ring.

(A1) Resin which has a cardo structure is not specifically limited, Conventionally well-known resin can be used. Especially, resin represented by a following formula (a-1) is preferable.

In formula (a-1), X ^a represents group represented by following formula (a-2). m1 represents the integer of 0-20.

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

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

Ring A in formula (a-3) represents the aliphatic ring which may be condensed with an aromatic ring, and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

Monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane etc. are mentioned as an aliphatic ring.

Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.

The aromatic ring which may be condensed to the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

Preferred 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 obtained by reacting tetracarboxylic dianhydride providing the residue Z ^a with a diol compound represented by the following formula (a-2a) in (A1) cardo resin is introduced

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

The diol compound represented by Formula (a-2a) can be manufactured by the following method, for example.

First, after replacing a hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with a group represented by -R ^a3 -OH by a general method if necessary, epichlorohydrin It is glycidylated using etc., and the epoxy compound represented by the following formula (a-2c) can be obtained.

Next, the diol compound represented by Formula (a-2a) can be obtained by making the epoxy compound represented by Formula (a-2c) react with acrylic acid or methacrylic acid.

In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 , and m2 are the same as described in formula (a-2). Ring A in formulas (a-2b) and (a-2c) is as described in formula (a-3).

In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to said method.

The following diol compounds are mentioned as a preferable example of the diol compound represented by Formula (a-2b).

In the formula (a-1), R ^a0 is a hydrogen atom or a group represented by -CO-Y ^a -COOH. Here, Y ^a represents the residue except the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorenedic anhydride, methyltetrahydroanhydride Phthalic acid, glutaric anhydride, etc. are mentioned.

In addition, in said formula (a-1), Z ^a represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, Biphenyl ether tetracarboxylic dianhydride etc. are mentioned.

In addition, in said formula (a-1), m represents the integer of 0-20.

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

The alkyl group which can be selected as R ^a4 in formula (a-4) is a C1-C10 alkyl group. By setting the number of carbon atoms included in the alkyl group within 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 is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, from the viewpoint of easiness of obtaining a cardo resin excellent in heat resistance. 3 is particularly preferred.

When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

As R ^a4 in formula (a-4), a hydrogen atom or a C1-C10 alkyl group is more preferable at the point which is easy to obtain Cardo resin excellent in heat resistance, respectively. As R ^a4 in the formula (a-4), a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable. It is preferable that several R<^a4> in Formula (a-4) is the same group from the point which preparation of highly purified tetracarboxylic dianhydride is easy.

m3 in Formula (a-4) represents the integer of 0-12. Purification of tetracarboxylic dianhydride can be facilitated by setting the value of m3 to 12 or less.

Since the purification of tetracarboxylic dianhydride is easy, 5 is preferable and, as for the upper limit of m3, 3 is more preferable.

1 is preferable and, as for the minimum of m3 from the chemical stability point of tetracarboxylic dianhydride, 2 is more preferable.

As for m3 in Formula (a-4), 2 or 3 is especially preferable.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^a5 and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a4 .

R ^a5 and R ^a6 represent a hydrogen atom or 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, still more preferably 1) from the viewpoint of easy purification of the tetracarboxylic dianhydride. It is preferable that it is an alkyl group of -4, Especially preferably 1-3), It is especially preferable that it is a hydrogen atom or a methyl group.

As the tetracarboxylic dianhydride represented by the formula (a-4), for example, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2′′-novonane-5,5 '',6,6''-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclopentanone 5'-spiro-2'-norbornane-5,5'',6, 6''-tetracarboxylic dianhydride"), methylnovonane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnovonane)-5,5'',6, 6''-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracar Acid dianhydride (alias "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride water"), methylnovonane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnovonane)-5,5'',6,6''-tetracarboxylic dianhydride Water, norbornane-2-spiro-α-cyclopropanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2 -Spiro-α-cyclobutanone-α′-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclo Heptanone-α′-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic dianhydride, norbonane-2-spiro-α-cyclooctanone-α′- Spiro-2''-Nobonane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2''- Norbonane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornane-5,5 '',6,6''-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2''-norbornane-5,5'',6,6 ''-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxyl Acid dianhydride, norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, novo I-2-spiro-α-cyclotetra decanone-α′-spiro-2′′-norbornane 5,5′′,6,6′′-tetracarboxylic dianhydride, norbonane-2-spiro-α-cyclopentadecanone-α′- Spiro-2''-Nobonane- 5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2 ''-Nobonane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''- norbornane-5,5'',6,6''-tetracarboxylic dianhydride, etc. are mentioned.

(A1) It is preferable that it is 1,000-40,000, and, as for the weight average molecular weight of cardo resin, it is more preferable that it is 2,000-30,000. By setting it as said range, sufficient heat resistance and film strength can be acquired while obtaining favorable developability.

Alkali-soluble resin (A) may contain alkali-soluble resin other than (A1) cardo resin. As such alkali-soluble resin, (A2) acrylic resin is mentioned.

(A2) As acrylic resin, the thing containing the structural unit derived from (meth)acrylic acid and/or the structural unit derived from (meth)acrylic acid ester is used. (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 formula (a-5), R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, any of linear, branched, and cyclic|annular form may be sufficient as this organic group.

Substituents other than the hydrocarbon group in the organic group of R ^a8 are not particularly limited as long as the effects of the present invention are not impaired, and a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group , acyl group, acyloxy group, sulfino group, sulfone group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkylthioether group, aryl ether group, an arylthioether group, an amino group (-NH2 _, -NHR, -NRR': R and R' each independently represent a hydrocarbon group), etc. are mentioned. The hydrogen atom contained in the said substitution may be substituted by the hydrocarbon group. In addition, linear, branched, and cyclic any may be sufficient as the hydrocarbon group contained in the said substituent.

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. In addition, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When an alkyl group is a linear or branched thing, 1-20 are preferable, as for the carbon atom number, 1-15 are more preferable, and 1-10 are especially preferable. Examples of preferred 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, isode and the like.

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

In addition, the (A2) acrylic resin may further superpose|polymerize other compounds other than (meth)acrylic acid and (meth)acrylic acid ester. As other compounds other than these, (meth)acrylamides, unsaturated carboxylic acids, aryl compounds, vinyl ethers, vinyl esters, styrenes, etc. are mentioned. These compounds can be used individually or in combination of 2 or more types.

As (meth)acrylamides, (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl ( Meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

Examples of the 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 aryl compound include aryl esters such as aryl acetate, aryl caproate, aryl caprylate, aryl laurate, aryl palmitate, aryl stearate, aryl benzoate, aryl acetoacetate, and aryl lactate; aryloxyethanol; have.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl. Ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether alkyl vinyl ethers such as; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorphenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; and the like.

Vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl. phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of styrene include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene , Alkyl styrene such as ethoxymethyl styrene and acetoxy methyl styrene; Alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene , halostyrenes such as pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene ; etc. are mentioned.

(A2) The quantity of the structural unit derived from (meth)acrylic acid in acrylic resin, and the quantity of the structural unit derived from (meth)acrylic acid ester will not be specifically limited if it is a range which does not impair the objective of this invention. (A2) 5-50 mass % is preferable with respect to the mass of acrylic resin, and, as for the quantity of the structural unit derived from (meth)acrylic acid in acrylic resin, 10-30 mass % is more preferable. Moreover, 10-95 mass % is preferable with respect to the mass of acrylic resin, and, as for the quantity of the structural unit derived from (meth)acrylic acid ester in (A2) acrylic resin, 30-90 mass % is more preferable.

(A2) The sum of the amount of the structural unit derived from (meth)acrylic acid in the acrylic resin and the amount of the structural unit derived from (meth)acrylic acid ester is not particularly limited as long as it does not impair the object of the present invention, (A2) 5-100 mass % is preferable with respect to the mass of acrylic resin, and 10-100 mass % is more preferable.

(A2) It is preferable that it is 2,000-200,000, and, as for the weight average molecular weight of acrylic resin, it is more preferable that it is 5,000-30,000. By setting it as said range, there exists a tendency for it to be easy to balance the film-forming ability of the photosensitive resin composition, and the developability after exposure.

50 mass % or more is preferable, as for the ratio of the mass of (A1) cardo resin which occupies the mass of alkali-soluble resin (A), 70 mass % or more is more preferable, 80 mass % or more is still more preferable, 90 mass % The above is particularly preferred, and 100% by mass is most preferred.

(A) It is preferable that it is 20-85 mass % with respect to the mass of the photosensitive resin composition except the mass of the organic solvent (S) mentioned later, and, as for content of alkali-soluble resin, it is more preferable that it is 25-75 mass %. By setting it as said range, the cured film which is hard to generate|occur|produce a gas can be formed, and it becomes easy to obtain the photosensitive resin composition excellent in developability.

<Photopolymerizable monomer (B)>

As the photopolymerizable monomer (B), a monomer having an ethylenically unsaturated group can be preferably used. The monomer having such 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, butoxymethyl Toxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acryl Rate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) ) acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) acrylates, and half (meth)acrylates of phthalic acid derivatives. These monofunctional monomers can be used individually or in combination of 2 or more types.

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, trimethylolpropane tri (meth) acrylate, glycerin di (meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane; 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether Di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth) Acrylates, urethane (meth) acrylates (that is, tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate), methylenebis (meth) acrylamide, ( Polyfunctional monomers, such as condensate of meth)acrylamide methylene ether, polyhydric alcohol, and N-methylol (meth)acrylamide, triacryl formal, etc. are mentioned. These polyfunctional monomers can be used individually or in combination of 2 or more types.

Among the monomers having an ethylenically unsaturated group, from the viewpoint of increasing the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition, a trifunctional or higher polyfunctional monomer is preferable, and a tetrafunctional or higher polyfunctional monomer is more It is preferable, and a polyfunctional monomer more than 5 functional is more preferable.

1-50 mass % is preferable with respect to the mass of the photosensitive resin composition except the mass of the organic solvent (S) mentioned later, and, as for content in the composition of a photopolymerizable monomer (B), 5-40 mass % is more preferable. By setting it as said range, there exists a tendency for it to be easy to balance a sensitivity, developability, and resolution.

<Photoinitiator (C)>

A photoinitiator (C) is not specifically limited, A conventionally well-known photoinitiator can be used.

Specifically as the photopolymerization initiator (C), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecyl) Phenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethane On, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-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, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid Ethyl, 4-dimethylamino butyl benzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1, 2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1 -Chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl Anthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylonitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2 -Mercaptobenzooxazole, 2-mercaptobenzodiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzo Phenone, 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, acetphenone, 2,2-diethoxyacetphenone, p-dimethylacetphenone, p-dimethylaminopropiophenone, dichloroacetphenone, trichloroacetphenone, p-tert-butylacetphenone, p-dimethylaminoacetphenone, p-tert -Butyltrichloroacetphenone, p-tert-butyldichloroacetphenone, α,α-dichloro-4-phenoxyacetphenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzo Suberon, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl) pentane, 1 ,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloro Rhomethyl)-s-triazine, 2-[2-(5-methylfuran-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(trichloromethyl)-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. These photoinitiators can be used individually or in combination of 2 or more types.

Among these, it is especially preferable from a point of a sensitivity to use the photoinitiator of an oxime system. Among the oxime-based photopolymerization initiators, particularly preferred are O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone, 1-[9 -Ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetyloxime), and 1,2-octanedione, 1-[4-(phenylthio) )-, 2-(O-benzoyloxime)] is mentioned.

It is also preferable to use the oxime type compound represented by following formula (c1) as a photoinitiator further.

(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.)

R ^c1 in formula (c1) is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferred examples when 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, an optionally substituted phenyl group, and an optionally substituted phenoxy group. Group, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, which may have a substituent Naphthoxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl which may have a substituent group, an amino group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. In addition, the number of carbon atoms of a substituent does not include the number of carbon atoms of a substituent which a substituent further has.

When R ^c1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c1 is an alkyl group, it may be linear or branched. Specific examples of when 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, an n-pentyl group, an 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- A decyl group, an isodecyl group, etc. are mentioned. In addition, 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, and a methoxypropyl group.

When R ^c1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples of when R ^c1 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. In addition, when R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples when R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples of when R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2, 2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples of when R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec- Butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxy group Carbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. In addition, when R ^c1 is a naphthylalkyl group, 11 to 20 carbon atoms are preferable, and 11 to 14 carbon atoms are more preferable. Specific examples when 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 when R ^c1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing inter-monocyclic or monocyclic rings and a benzene ring. When the heterocyclyl group is a condensed ring, the number of rings is assumed to be up to three. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyrazine, pyrazine. , pyrimizine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline , phthalazine, cinnoline, and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 20 carbon atoms. An actual group, a phenyl group which may have a substituent, a benzoyl group which 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, a naphthoyl group which may have a substituent, a substituent and a naphthylalkyl group and heterocyclyl group having 11 to 20 carbon atoms which may have Specific examples of these preferred organic groups are the same as R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butylamino group , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoyl amino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group. can

When the phenyl group, naphthyl group, and heterocyclyl group included 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 2 to 7 carbon atoms. A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a monoalkylamino group having 1 to 6 carbon atoms and a dialkylamino group having an alkyl group, 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 included in R ^c1 further have a substituent, the number of the substituents is not limited as long as it does not impair the object of the present invention, but 1 to 4 are preferable. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

In R ^c1 , from the viewpoint of being chemically stable and having few steric hindrances and easy synthesis of an oxime ester compound, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 7 carbon atoms A group selected from the group consisting of a saturated aliphatic acyl group is preferred, an alkyl having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

The position where R ^c1 is bonded to the phenyl group is the 4th position when the bonding hand of the phenyl group and the main skeleton of the oxime ester compound is the 1st position and the methyl group is the 2nd position with respect to the phenyl group to which ^Rc1 is bonded. Position 5 is preferable, and position 5 is more preferable. Moreover, the integer of 0-3 is preferable, as for n1, the integer of 0-2 is more preferable, 0 or 1 is especially preferable.

R ^c2 is an optionally substituted phenyl group or an optionally substituted carbazolyl group. Further, 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 substituents of the phenyl group or the carbazolyl group are not particularly limited as long as they do not impair the object of the present invention. Examples of the preferable substituent which the phenyl group or the carbazolyl group may have on a carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 3 carbon atoms. A cycloalkoxy group having ~10, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, The phenoxy group which may have a substituent, the phenylthio group which may have a substituent, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the carbon which may have a substituent A phenylalkyl group having 7 to 20 atoms, 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, and a substituent Substituted with a naphthoyloxy group, 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, or an organic group of 1 or 2 an amino group, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

When R ^c2 is a carbazolyl group, examples of a preferable substituent that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and saturation having 2 to 20 carbon atoms. Aliphatic acyl group, alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, 7 to carbon atoms which may have a substituent 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, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a substituent The heterocyclyl group which you may have, the heterocyclyl carbonyl group which may have a substituent, etc. are 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.

For specific examples of the substituent which the phenyl group or the carbazolyl group may have, 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, a phenylalkyl group which may have a substituent; The naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with 1 or 2 organic groups are the same as R ^c1 .

In R ^c2 , examples of the substituent when the phenyl group, naphthyl group and heterocyclyl group included in the substituent of the phenyl group or the carbazolyl group have a substituent include an alkyl group having 1 to 6 carbon atoms; Alkoxy group of ~6; Saturated aliphatic acyl group of 2-7 carbon atoms; Alkoxycarbonyl group of 2-7 carbon atoms; Saturated aliphatic acyloxy group of 2-7 carbon atoms; Phenyl group; Naphthyl group; Benzoyl group; Naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; an alkyl group having 1 to 6 carbon atoms; Monoalkylamino group which has; Dialkylamino group which has a C1-C6 alkyl group; Morpholin-1-yl group; Piperazin-1-yl group; Halogen; Nitro group; Cyano group is mentioned. When the phenyl group, naphthyl group and heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group have additional substituents, the number of the substituents is not limited as long as it does not impair the object of the present invention, but 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 , a group represented by the following formula (c2) or (c3) is preferable, and a group represented by the following formula (c2) is more preferable, from the viewpoint of easiness of obtaining a photopolymerization initiator having excellent sensitivity, the group represented by the following formula (c2) As the group represented by c2), a group in which A is S is particularly preferred.

(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 0-4.)

(R ^c5 and R ^c6 are each a monovalent organic group.)

When R ^c4 in formula (c2) is an organic group, it may be selected from various organic groups within a range that does not impair the object of the present invention. Preferred examples of when R ^c4 is an organic group in formula (c2) include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; Alkoxycarbonyl group of 2-7; Saturated aliphatic acyloxy group of 2-7 carbon atoms; Phenyl group; Naphthyl group; Benzoyl group; Naphthoyl group; Alkyl group of 1-6 carbon atoms, Morpholin-1-yl group, pipette A benzoyl group substituted by a group selected from the group consisting of a razin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; polyin-1-yl group; piperazin-1-yl group; halogen; nitro group; and cyano group.

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

Moreover, in Formula (c2), the integer of 0-3 is preferable, as for n3, the integer of 0-2 is more preferable, It is especially preferable that it is 0 or 1. When n3 is 1, it is preferable that the bonding position of R ^c4 is para to the hand at which the phenyl group to which R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom.

In formula (c3), R ^c5 may be selected from various organic groups within a range that does not impair the object of the present invention. Preferred examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a substituent group The phenyl group which may have, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the C7-C20 phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, even if it has a substituent naphthoyl group, optionally naphthoxycarbonyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, optionally substituted heterocyclyl group, and optionally substituted heterocyclyl carbo nyl group etc. are mentioned.

In 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 formula (c3) is not particularly limited as long as it does not impair the object of the present invention, and may be selected from various organic groups. Specific examples of the group preferable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclyl group. As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, the naphthyl group and the heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 have an additional substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon A saturated aliphatic acyl group having 2 to 7 atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, carbon and a dialkylamino group having an alkyl group having 1 to 6 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 included in R ^c4 , R ^c5 or R ^c6 have additional substituents, the number of the substituents is not limited as long as it does not impair the object of the present invention, but 1 to 4 are preferable. do. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 have 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.

When p is 0, the oxime ester compound represented by Formula (c1) can be synthesize|combined according to following Scheme 1, for example. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (c1-2), and the following formula (c1- The ketone compound represented by 3) is obtained, and the obtained ketone compound (c1-3) is oximeated with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), and then the formula (c1-4) The oxime ester compound represented by the following formula (c1-7) can be obtained by acylating the hydroxyl group in the oxime compound of. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c1-5) or an acid halide (R ^c3 COHal, Hal is a halogen) represented by the following formula (c1-6) is used. it is preferable In addition, in the following formula (c1-2), Hal is halogen, and R in the following formulas (c1-1), (c1-2), (c1-3), (c1-4) and (c1-7) ^c1 , R ^c2 , R ^c3 and n1 have the same formula (c1).

<Scheme 1>

When n2 is 1, the oxime ester compound represented by Formula (c1) can be synthesize|combined according to the following scheme 2, for example. Specifically, a nitrous acid ester represented by the following formula (c2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) is reacted with a ketone compound represented by the following formula (c2-1) in the presence of hydrochloric acid to obtain a ketoxime compound represented by the following formula (c2-3), and then acylating a hydroxyl group in the ketoxime compound represented by the following formula (c2-3) to an oxime ester represented by the following formula (c2-6) compound can be obtained. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c2-4) or an acid hydride (R ^c3 COHal, Hal is a halogen) represented by the following formula (c2-5) is used. desirable. In addition, in the following formulas (c2-1), (c2-3), (c2-4), (c2-5) and (c2-6), R ^c1 , R ^c2 , R ^c3 , and n1 are ) is the same as

<Scheme 2>

In addition, in the oxime ester compound represented by the formula (c1), when n2 is 1, R ^c1 is a methyl group, and R ^c1 is bonded to the para position with respect to the methyl group bonded to the benzene ring to which R ^c1 is bonded, for example, For example, the compound represented by the following formula (c2-7) can also be synthesized by oximation and acylation in the same manner as in Scheme 1. In addition, in the following formula (c2-7), R ^c2 is the same as the formula (c1).

The following PI-1 to PI-42 are mentioned as a compound especially preferable among the oxime ester compounds represented by Formula (c1).

Moreover, the oxime ester compound represented by a following formula (c4) is also preferable as a photoinitiator.

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, 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, and R ^c8 and R ^c9 are may combine with each other to form a ring, R ^c10 is a monovalent organic group, 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, and n4 is It is an integer from 0 to 4, and n5 is 0 or 1)

Here, as an oxime compound for manufacturing the oxime ester compound of Formula (c4), the compound represented by a following formula (c5) is preferable.

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

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) _n5 - on the fluorene ring in formula (c4). In formula (c4), the bonding position of R ^c7 to the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has one or more R ^c7 , one or more R ^c7 is bonded to the 2-position in the fluorene ring from the point of facilitating the synthesis of the compound represented by the formula (c4). it is preferable When there are a plurality of R ^c7 , the plurality of R ^c7 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 impair the object of the present invention, and is appropriately selected from various organic groups. Preferred examples when 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, an optionally substituted phenyl group, and an optionally substituted phenoxy group. Group, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, which may have a substituent Naphthoxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent , an optionally substituted heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^c7 is an alkyl group, 1-20 are preferable and, as for carbon atom number of an alkyl group, 1-6 are more preferable. Further, when R ^c7 is an alkyl group, it may be linear or branched. Specific examples when R ^c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an 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- A decyl group, an isodecyl group, etc. are mentioned. In addition, 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, and a methoxypropyl group.

When R ^c7 is an alkoxy group, 1-20 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. Further, when R ^c7 is an alkoxy group, it may be linear or branched. Specific examples of when R ^c7 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. In addition, 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 a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3-6 are more preferable. Specific examples when R ^c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^c7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples when R ^c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2, 2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples when R ^c7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoylox group Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c7 is an alkoxycarbonyl group, 2-20 are preferable and, as for carbon atom number of an alkoxycarbonyl group, 2-7 are more preferable. Specific examples when R ^c7 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec- Butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxy group carbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, 7-20 are preferable and, as for carbon atom number of a phenylalkyl group, 7-10 are more preferable. Moreover, when R ^<c7> is a naphthylalkyl group, 11-20 are preferable and, as for carbon atom number of a naphthylalkyl group, 11-14 are more preferable. Specific examples when 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 when R ^c7 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, R ^c7 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-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing such inter-monocyclic or monocyclic rings and a benzene ring. When the heterocyclyl group is a condensed ring, the number of rings is assumed to be up to three. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyrizine, pyrazine, Pyrimizine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, and phthalazine, cinnoline, quinoxaline, piperizine, piperazine, morpholine, piperazine, tetrahydropyran and tetrahydrofuran. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with an organic group of 1 or 2, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 21 carbon atoms. An actual group, a phenyl group which may have a substituent, a benzoyl group which 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, a naphthoyl group which may have a substituent, a substituent and a naphthylalkyl group and heterocyclyl group having 11 to 20 carbon atoms which may have Specific examples of these preferred organic groups are the same as R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butylamino group , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoyl amino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group. have.

When the phenyl group, naphthyl group and heterocyclyl group included in R ^c7 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 2 to 7 carbon atoms. A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a monoalkylamino group having 1 to 6 carbon atoms and a dialkylamino group having an alkyl group, 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 ^c7 further have a substituent, the number of the substituents is not limited as long as it does not impair the object of the present invention, but 1 to 4 are preferable. When the phenyl group, naphthyl group and 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, when R ^c7 is a nitro group or a group represented by R ^c12 -CO-, the sensitivity tends to improve, so it is preferable. R ^c12 is not particularly limited as long as it does not impair the object of the present invention and may be selected from various organic groups. Examples of the group preferable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclyl group. As R ^c12 , of these groups, a 2-methylphenyl group, a thiophen-2-yl group and an α-naphthyl group are particularly preferable. Moreover, when R ^c7 is a hydrogen atom, since transparency tends to become favorable, it is preferable. In addition, when R ^c7 is a hydrogen atom and R ^c10 is a group represented by a formula (c4a) or a formula (c4b) described later, transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 each represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may combine with each other to form a ring. Among these groups, a chain alkyl group which may have a substituent as R ^c8 and R ^c9 is preferable. When R ^c8 and R ^c9 are a chain alkyl group 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 a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of when R ^c8 and R ^c9 are a chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a 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, isono A nyl group, an n-decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c8 and R ^c9 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c8 and R ^c9 are a chain alkyl group having a substituent, the number of carbon atoms in 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. It is preferable that the chain|strand-chain alkyl group which has a substituent is linear.

The substituent which an alkyl group may have is not specifically limited if it is a range which does not impair the objective of this invention. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group and an alkoxycarbonyl group. A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen 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 preferred examples when R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as preferred examples 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, and linear is preferable. 1-10 are preferable and, as for carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

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

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

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of 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 benzene rings included in the aromatic hydrocarbon group is not particularly limited and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 do.

Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.

When R ^c8 and R ^c9 are an aliphatic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

When R ^c8 and R ^c9 are a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group obtained by condensing between such monocyclic rings or such a monocyclic ring and a benzene ring . When the heterocyclyl group is a condensed ring, the number of rings is assumed to be up to three. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Mijin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr talazine, cinnoline, quinoxaline, piperizine, piperazine, morpholine, piperizine, tetrahydropyran, tetrahydrofuran, and the like.

R ^c8 and R ^c9 may combine with each other to form a ring. The group consisting of a ring formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

When the group formed by bonding R ^c8 and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with the cycloalkylidene 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, a pyridine ring, A pyrazine ring, a pyrimijin ring, etc. are mentioned.

Among the above-described R ^c8 and R ^c9 , preferred examples of the group include a group represented by the formula-A ¹ -A ² . In the formula, A ¹ is a straight-chain alkylene group, and A ² is, for example, an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

1-10 are preferable and, as for carbon atom number of the linear alkylene group of A< ¹ >, 1-6 are more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and linear is preferable. 1-10 are preferable and, as for carbon atom number of an alkoxy group, 1-6 are more preferable. When ^A2 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 A2 is ^a halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable and, as for the halogen atom contained in a halogenated alkyl group, a fluorine atom, a chlorine atom, and a bromine atom are more preferable. The halogenated alkyl group may be linear or branched, and linear is preferable. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^c8 and R ^c9 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups R ^c8 and R ^c9 have as a substituent.

Preferred specific examples of R ^c8 and R ^c9 include an alkyl group such as an 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 group -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 Alkoxyalkyl groups, such as an actual group, 7-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-pentyl group, 6-cyano n-hexyl group, 7-cyano n-heptyl group, and cyanoalkyl groups such as 8-cyano n-octyl group; 2-phenylethyl group, 3-phenyl group -n-propyl 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 phenylalkyl groups such as; 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 group Cycloalkylalkyl groups such as pentyl-n-pentyl group, 6-cyclopentyl-n-hexyl group, 7-cyclopentyl-n-heptyl group and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group; 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7- Methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n -Butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group and 8-ethoxycarbonyl-n-ox Alkoxycarbonylalkyl groups such as tyl 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 and halogenated alkyl groups such as -bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Preferred groups among the above as R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5-heptafluoro-n-phene it's til

Examples of the preferable organic group for R ^c10 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group optionally having a substituent, and a substituent like R ^c7 The phenoxy group which may have, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, 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 naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, and a substituent and a heterocyclyl group, optionally a heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are as described for R ^c7 . Moreover, as R<^c10> , a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ^<c7> may have.

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

Further, as R ^c10 , a group represented by -A ³ -CO-OA ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. ^A4 is a monovalent organic group, and it is preferable that it is a monovalent|monohydric hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and linear is preferable. When ^A3 is an alkylene group, 1-10 are preferable, as for carbon atom number of an alkylene group, 1-6 are more preferable, and 1-4 are especially preferable.

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

Preferred specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxycarbo Nylethyl 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, etc. are mentioned.

Although R ^{c10 has been described above, as R c10 ,} a group represented by the following formula (c4a) or (c4b) is preferable.

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

Examples of the organic group for R ^c13 and R c14 in the formula ( ^c4a ) are the same as for R ^c7 . R ^c13 is preferably an alkyl group or a phenyl group. When R ^c13 is an alkyl group, 1-10 are preferable, as for the number of carbon atoms, 1-5 are more preferable, 1-3 are especially preferable, and 1 is the most preferable. 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. Preferred examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group and a 1,2,3,4-tetrahydronaphthalen-5-yl group. can In said formula (c4a), n6 is an integer of 0-4, It is preferable that it is 0 or 1, It is more preferable that it is 0.

In the formula (c4b), R ^c15 is an organic group. Examples of the organic group include the same groups as the organic group described for R ^c7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1-10 are preferable, as for carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. R ^c15 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and among these, a methyl group is more preferable.

In said formula (c4b), n8 is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable. In said formula (c4b), n9 is 0-(n8+3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, 0 is especially preferable. In said formula (c4b), n7 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, 1 or 2 is especially preferable.

In formula (c4), R ^c11 is a hydrogen atom, an optionally substituted C1-C11 alkyl group, or an optionally substituted aryl group. When R ^c11 is an alkyl group, a phenyl group, a naphthyl group, etc. are preferably exemplified as the substituent which may be included. Moreover, as a substituent which you may have when R ^<c7> is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

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

The compound represented by the formula (c4) converts the oxime group (>C=N-OH)) contained in the compound represented by the formula (c5) described above into an oxime ester group represented by >C=NO-COR ^c11 It is manufactured by a method comprising the process of: R ^c11 is the same as R ^c11 in formula (c4).

The conversion of an oxime group (>C=N-OH)) to an oxime ester group represented by >C=NO-COR ^c11 is achieved by reacting the compound represented by the above formula (c5) with an acylating agent. The acylating agent giving the acyl group represented by -COR ^c11 includes an acid anhydride represented by (R ^c11 CO) ₂ O and an acid halide represented by R ^c11 COHal (Hal is a halogen atom).

When n5 is 0, the compound represented by the general formula (c4) can be synthesized according to, for example, Scheme 3 below. In Scheme 3, the 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, in the fluorene derivative represented by formula (c3-1), a substituent R ^c7 is introduced into the fluorene derivative in which the 9-position is substituted with R ^c8 and R ^c9 by a known method. can be obtained by A fluorene derivative substituted with R ^c8 and R ^c9 at position 9 is, for example, when R ^c8 and R ^c9 are an alkyl group, as described in Japanese Unexamined Patent Application Publication No. Hei 06-234668, an aproton in the presence of an alkali metal hydroxide It can be obtained by reacting fluorene with an alkylating agent in a polar organic solvent. In addition, 9,9- by adding 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 to an organic solvent solution of fluorene to carry out an alkylation reaction. Alkyl-substituted fluorene can be obtained.

The fluorene derivative represented by the formula (c3-3) can be obtained by introducing an acyl group represented by -CO-R ^c10 to the fluorene derivative represented by the formula (c3-1) according to a Friedel-Crafts acylation reaction. . The acylating agent for introducing the 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), Hal is a halogen atom. The position at which the acyl group is introduced onto the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction or by performing protection and deprotection at a position different from the acylation position.

Next, in the obtained fluorene derivative represented by formula (c3-3), the group represented by -CO-R ^c10 is converted into a group represented by -C(=N-OH)-R ^c10 , and formula (c3-4) to obtain an oxime compound represented by 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 oximation with hydroxylamine is preferable. The oxime compound of formula (c3-4) and the acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5) or the acid halide (R ^c11 COHal, Hal) represented by the following formula (c3-6) is a halogen atom) to obtain a compound represented by the following formula (c3-7).

On the other hand, in 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 Formula (c4).

In Scheme 3, R ^c10 contained in each of the formulas (c3-2), (c3-3), and (c3-4) may be the same or different. That is, R ^c10 in the formulas (c3-2), (c3-3), and (c3-4) may undergo chemical modification in the synthesis process shown as Scheme 3. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. Chemical formulas that R ^c10 may accept are not limited to these.

<Scheme 3>

When n5 is 1, the compound represented by formula (c4) can be synthesized according to, for example, Scheme 4 below. In Scheme 4, a fluorene derivative represented by the following formula (c4-1) is used as a raw material. The fluorene derivative represented by the formula (c4-1) is an acyl represented by -CO-CH ₂ -R ^c10 by Friedel-Crafts reaction to the compound represented by the formula (c3-1) by the same method as in Scheme 3 It can be obtained by introducing a group. The acylating agent is preferably a carboxylic acid halide represented by the formula (c3-8): Hal-CO-CH ₂ -R ^c10 . Next, the methylene group present between R ^c10 and the carbonyl group in the compound represented by the formula (c4-1) is oximelated to obtain a ketooxime compound represented by the following formula (c4-3). The method for oximating the methylene group is not particularly limited, but a method of reacting a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (c4-2) in the presence of hydrochloric acid 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 an acid halide represented by the following formula (c4-5) (R ^c11 COHal, Hal is a halogen atom) can be reacted to obtain a compound represented by the following formula (c4-6). On the other hand, 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 in formula (c4). When n5 is 1, there exists a tendency which generation|occurrence|production of the foreign material in the pattern formed using the photosensitive resin composition containing the compound represented by Formula (c4) can be reduced more.

In Scheme 4, R ^c10 contained in each of the formulas (c3-8), (c4-1), and (c4-3) may be the same or different. That is, R ^c10 in the formulas (c3-8), (c4-1), and (c4-3) may undergo chemical modification in the synthesis process represented by Scheme 4. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. The chemical formula that R ^c10 may accept is not limited to these.

<Scheme 4>

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

It is preferable that it is 0.5-30 mass % with respect to the mass of the photosensitive resin composition except the mass of the organic solvent (S) mentioned later, and, as for content of a photoinitiator (C), it is more preferable that it is 1-20 mass %. By making content of a photoinitiator (C) into said range, the photosensitive resin composition which the defect of a pattern shape does not produce easily can be obtained.

Moreover, you may combine a photoinitiator adjuvant with a photoinitiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxy Anthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto Thiol compounds, such as 5-methoxybenzothiazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, etc. are mentioned. These photoinitiators can be used individually or in combination of 2 or more types.

<Polyfunctional crosslinkable compound (D)>

The photosensitive resin composition contains a polyfunctional crosslinkable compound (D). A polyfunctional crosslinkable compound (D) is a crosslinkable compound provided with a some epoxy group or oxetanyl group in 1 molecule. In addition, the epoxy equivalent or oxetanyl equivalent of a polyfunctional crosslinking|crosslinked compound (D) is 50-350 g/eq.

Since the photosensitive resin composition contains a polyfunctional crosslinkable compound having an epoxy equivalent or an oxetanyl equivalent in this range, when a cured film is formed using the photosensitive resin composition, the alkali-soluble resin (A) is densely crosslinked and separated from the cured film It is easy to suppress the generation of gas.

In addition, from the viewpoint of more notably expressing these effects, the epoxy equivalent or oxetanyl equivalent of the polyfunctional crosslinkable compound (D) is more preferably 60 to 320 g/eq, and 70 to 300 g/eq It is more preferable, and it is especially preferable that it is 75-280 g/eq.

From the viewpoint of crosslinking reactivity when forming a cured film, the polyfunctional crosslinkable compound (D) preferably contains an epoxy compound having two or more epoxy groups per molecule, and contains an epoxy compound having three or more epoxy groups per molecule. It is more preferable to

The content of the epoxy compound having two or more epoxy groups per molecule in the polyfunctional crosslinkable compound (D) is preferably 50 mass % or more, more preferably 70 mass % or more, still more preferably 80 mass % or more, 90 Mass % or more is particularly preferred, and 100 mass % is most preferred.

As the polyfunctional crosslinkable compound (D), only when the epoxy equivalent or oxetanyl equivalent is within a predetermined range, a polyfunctional epoxy compound or a polyfunctional oxetane compound conventionally blended in various curable compositions may be used. can

The molecular weight of the polyfunctional epoxy compound or 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 5,000 or less, more preferably 4,500 or less, from the viewpoint of less steric hindrance and easy crosslinking between molecular chains of alkali-soluble resin (A). , 4,000 or less are particularly preferred.

Although the lower limit of this molecular weight is not specifically limited, For example, it is 150 or more.

The polyfunctional crosslinkable compound (D) may be a compound containing an aromatic group or a compound not containing an aromatic group. It is preferable that the polyfunctional crosslinking|crosslinked compound (D) is a compound which does not contain an aromatic group at the point which can easily obtain the photosensitive resin composition which can form the hardened|cured material with little gas generation.

As an example of a preferable polyfunctional crosslinking|crosslinked compound (D), the polyfunctional alicyclic epoxy compound which has an alicyclic epoxy group is mentioned. Specific examples of the alicyclic epoxy compound include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl) ) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxyl rate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclo Hexane carboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylene A polyfunctional epoxy compound having di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate) and tricyclodeceneoxide groups of glycol, the following formula (d1-1) to The compound represented by (d1-5) is mentioned.

These alicyclic epoxy compounds may be used individually or may be used in mixture of 2 or more types.

(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 each independently selected from the group consisting of a hydrogen atom, a halogen atom and an organic group. It's a gimmick.)

Examples of the linking group Z include a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, and a divalent group selected from the group consisting of -C(CF ₃ ) ₂ - and -R ^a19 -O-CO-, a group in which a plurality of these groups are bonded, and the like.

Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. 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, and a trimethylene group. 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-cyclohexylene group. cycloalkylene groups (including a cycloalkylidene group), such as group, 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

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

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

(In formula (d1-3), R ^d1 to R ^d10 are a group 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.)

(In formula (d1-4), R ^d1 to R ^d12 are a group 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.)

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

In formulas (d1-1) to (d1-5), when R ^a1 to Ra ¹⁸ are an organic group, the organic group is not particularly limited as long as it does not impair the object of the present invention. The group may be a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom together with a carbon atom and a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

The organic group is preferably a group consisting of a hydrocarbon group, a carbon atom, a hydrogen atom and an oxygen atom, a group consisting of a halogenated hydrocarbon group, a carbon atom, an oxygen atom and a halogen atom, a group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1-20 are preferable, as for carbon atom number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

Specific examples of the hydrocarbon group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexa Chain alkyl groups such as decyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1 chain alkenyl groups such as -n-butenyl, 2-n-butenyl and 3-n-butenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; phenyl; , 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 group; aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group and β-naphthylethyl group.

Specific examples of the halogenated hydrocarbon group include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2,2-trifluoro Halogenated chain alkyl groups such as ethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluorpentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group and perfluordecyl group ; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group and 4-bro Halogenated cycloalkyl group such as mocyclohexyl 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, 4-fluorophenyl group, etc. of halogenated aryl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, halogenated aralkyl groups such as 3-fluorophenylmethyl group and 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom and an oxygen atom include a hydroxy chain alkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group and a 4-hydroxy-n-butyl group; Halogenated cycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 -dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group and 3,5-dihydroxyphenyl group hydroxyaryl groups such as; 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 chain alkoxy groups such as , n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-eicosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyl Chain alkenyloxy groups such as oxy group (aryloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group and 3-n-butenyloxy group; phenoxy group, o-tolyloxy group, m-tol Lyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and Aryloxy groups such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, β-naphthylethyloxy group, etc. of aralkyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethyl 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 group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group and 4-n-propoxy-n- wealth Alkoxyalkyl groups such as tyl group; methoxymethoxy group, ethoxy methoxy group, n-propoxymethoxy group, 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, 4-methoxy-n-butyloxy group, 4-ethoxy- Alkoxy alkoxy groups such as n-butyloxy group and 4-n-propoxy-n-butyloxy group; Alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group and 4-methoxyphenyl group; Alkoxyaryloxy groups such as oxyphenoxy group, 3-methoxyphenoxy group and 4-methoxyphenoxy group; formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, no aliphatic acyl groups such as nanoyl and decanoyl; aromatic acyl groups such as benzoyl, α-naphthoyl and β-naphthoyl; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n -chain alkyl such as butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group and n-decyloxycarbonyl group oxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group and β-naphthoxycarbonyl group; formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, aliphatic acyloxy groups such as hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group and decanoyloxy group; aromatic acyl groups such as benzoyloxy group, α-naphthoyloxy group and β-naphthoyloxy group is an oxy group.

R ^d1 to R ^d18 are each independently preferably a group 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, especially a cured film having excellent mechanical properties From the viewpoint of easy formation, it is more preferable that all of R ^a1 to R ^a18 are hydrogen atoms.

In formulas (d1-2) to (d1-5), R ^d1 to R ^d12 are the same as R ^d1 to R ^d12 in formula (d1-1). In formulas (d1-2) and (d1-4), as a divalent group formed when R ^d2 and R ^d10 are bonded to each other, for example, -CH ₂ -, -C(CH ₃ ) ₂ - can be heard. Examples of the divalent group formed when R ^d2 and R ^d8 are bonded to each other in formula (P1-3) include -CH ₂ - and -C(CH ₃ ) ₂ -.

Among the alicyclic epoxy compounds represented by formula (d1-1), specific examples of preferred compounds include alicyclic epoxy compounds represented by the following formulas (d1-1a), (d1-1b) and (d1-1c); , 2,2-bis(3,4-epoxycyclohexan-1-yl)propane [=2,2-bis(3,4-epoxycyclohexyl)propane]; and the like.

Among the alicyclic epoxy compounds represented by formula (d1-2), specific examples of preferred compounds include bicyclononadiene diepoxide or dicyclononadiene diepoxide represented by the following formula (d1-2a).

Among the alicyclic epoxy compounds represented by formula (d1-3), specific examples of preferred compounds include S spiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6,2'-oxirane] can

Among the alicyclic epoxy compounds represented by formula (d1-4), specific examples of preferred compounds include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, and 1-methyl-4-(3-methyloxirane-2- yl)-7-oxabicyclo[4.1.0]heptane etc. are mentioned.

Among the alicyclic epoxy compounds represented by Formula (d1-5), 1,2,5,6-diepoxycyclooctane etc. are mentioned as a specific example of a preferable compound.

Examples of the epoxy compound other than the alicyclic epoxy compound described above that can be preferably used as the polyfunctional crosslinkable compound (D) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AD type. Bifunctional epoxy resins such as epoxy resins, naphthalene type epoxy resins and biphenyl type epoxy resins; phenol novolac type epoxy resins, brominated phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, bisphenol A novolak type epoxy resin and novolak epoxy resins such as bisphenol AD novolak type epoxy resins; cyclic aliphatic epoxy resins such as epoxides of dicyclopentadiene type phenol resins; aromatic epoxy resins such as epoxides of naphthalene type phenol resins; Bis[4-(glycidyloxy)phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9- bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9, Contains epoxy groups such as 9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene and 9,9-bis(6-glycidyloxynaphthalen-yl)-9H-fluorene Fluorene compounds; Glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; Tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethacylyl Glycidylamine type epoxy resins, such as rendiamine and tetraglycidylbisaminomethylcyclohexane; Heterocyclic epoxy resins, such as triglycidyl isocyanurate; Phloroglycinol triglycidyl ether, trihydroxybi Phenyl 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-[ Trifunctional epoxy resins such as 4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; tetrafunctional epoxy resins such as tanetetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether and tetraglycidoxybiphenyl; 2,2-bis(hydroxymethyl)-1- 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of butanol. A 1,2-epoxy-4-(2-oxiranyl)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 preferably used as the polyfunctional crosslinkable compound (D) include bis-1-ethyl-3-oxetanylmethyl ether and 1,4-bis-3-ethyloxetan-3-ylmethoxymethyl. and bifunctional or more than bifunctional oxetane compounds, such as benzene.

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

(In formula (d1-6), R ^d20 to R ^d22 are linear, branched or cyclic alkylene group, allylene group, -O-, -C(=O)-, -NH-, and combinations thereof. E ¹ to E ³ are epoxy group, oxetanyl group, ethylenically unsaturated group, alkoxysilyl group, isocyanate group, blocked isocyanate group, thiol group, carboxyl group, hydroxyl group and succinic anhydride group It is at least ¹ type of substituent or hydrogen atom selected from ^the group consisting of

In the formula (d1-6), it is preferable that at least two of the 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). and it is more preferable that all are groups represented by the following formula (d1-6a), respectively. It is preferable that the groups represented by several formula (d1-6a) couple|bonded with one compound are the same group.

-L-Cｄ （ ^{ｄ１－６ａ} ）

(In formula (d1-6a), L is a linear, branched or cyclic alkylene group, an allylene group, -O-, -C(=O)-, -NH-, and a group consisting of combinations thereof, and C ^d is at least one member 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 each other 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 allylene group as L is 5 to 10 carbon atoms. An allylene group of In formula (d1-6a), L is a group consisting of a linear C1-C3 alkylene group, a phenylene group, -O-, -C(=O)-, -NH-, and combinations thereof. Preferably, at least one of a linear C1-C3 alkylene group such as a methylene group and a phenylene group, or a combination of these and at least one of -O-, -C(=O)- and NH- It is preferable to be a group consisting of

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 (a structure having an alicyclic epoxy group). When forming, the organic group represented by a following formula (d1-6b) or a formula (d1-6c) is mentioned.

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

Hereinafter, examples of the epoxy compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group and an alicyclic epoxy group are shown as examples of the compound represented by the formula (d1-6), not.

Moreover, as a compound which can be used preferably as a polyfunctional crosslinking|crosslinked compound (D), the siloxane compound which has two or more glycidyl groups in a molecule|numerator (hereinafter also simply described as a "siloxane compound") is mentioned.

The siloxane compound is a compound having a siloxane skeleton constituted by 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 cyclic siloxane skeleton, polysiloxane skeleton (for example, linear or branched silicone (linear or branched polysiloxane), cage or ladder polysilsesquioxane) etc.) and the like.

As a siloxane compound, especially, the compound (henceforth "cyclic siloxane") which has a cyclic siloxane skeleton represented by a following formula (d1-7) is preferable.

In formula (d1-7), R ^d24 and R ^d25 represent a monovalent group or an alkyl group containing a glycidyl group. However, in the compound represented by the formula (d1-7), at least two of x1 R ^d24 and x1 R ^d25 are monovalent groups containing a glycidyl group. In addition, x1 in Formula (d1-7) represents an integer of 3 or more. In the compound represented by formula (d1-7), R ^d24 and R ^d25 may be the same or different. In addition, a plurality of R ^d24 may be the same or different. A plurality of R ^d25 may be the same or different.

The monovalent group containing the glycidyl group is preferably a glycidyl ether group represented by -DOR ^d26 [D represents an alkylene group, R ^d26 represents a glycidyl group]. Examples of the D (alkylene group) include a linear or branched alkylene group having 1 to 18 carbon atoms, such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. have.

Examples of the alkyl group include 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. A linear or branched alkyl group is mentioned.

x1 in Formula (d1-7) represents an integer of 3 or more, and an integer of 3-6 is preferable at the point which is excellent in the crosslinking reactivity at the time of forming a cured film especially.

The number of the glycidyl groups which a siloxane compound has in a molecule|numerator is 2 or more, From the point excellent in the crosslinking reactivity at the time of forming a cured film, 2-6 pieces are preferable, Especially preferably, it is 2-4 pieces.

In addition to the siloxane compound represented by the formula (d1-7), the photosensitive resin composition contains an alicyclic epoxy group-containing cyclic siloxane, an alicyclic epoxy group-containing silicone resin described in Japanese Patent Application Laid-Open No. 2008-248169, and one molecule described in Japanese Patent Application Laid-Open No. 2008-19422 You may contain the compound which has siloxane frame|skeleton, such as organopolysilsesquioxane resin which has at least two epoxy functional groups in it.

More specifically, as a siloxane compound, the cyclic siloxane etc. which have two or more glycidyl groups in the molecule|numerator represented by the following formula are mentioned. In addition, as a siloxane compound, "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" are, for example, a brand name, for example. Commercial items, such as (above, the Shin-Etsu Chemical Industries make) can be used.

It is preferable that it is 1-40 mass % with respect to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) mentioned later, and, as for content of a polyfunctional crosslinkable compound (D), it is more preferable that it is 3-30 mass %. . By making content of a polyfunctional crosslinking|crosslinked compound (D) into said range, the photosensitive resin composition which can form a cured film with little gas generation can be obtained easily.

It is preferable that ratio of content [g] of alkali-soluble resin (A) in the photosensitive resin composition and content [g] of polyfunctional crosslinking compound (D) exists in the range of 15:1-0.5:1, 10:1 It is more preferable to exist in the range of -1:1, and it is more preferable to exist in the range of 8:1-2:1. By using alkali-soluble resin (A) and polyfunctional crosslinking|crosslinked compound (D) in the ratio within this range, the photosensitive resin composition which can form a cured film with little gas generation in particular can be easily obtained.

<Colorant (E)>

The photosensitive resin composition may contain the coloring agent (E). Although it does not specifically limit as a coloring agent (E), For example, in the color index (C.I.; issued by The Society of Dyersand Colorists), a compound classified as a pigment, specifically, the following color index (C.I.) It is preferable to use what is assigned a number.

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

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

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

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

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

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

Moreover, the photosensitive resin composition may contain the light-shielding agent as a coloring agent (E). The photosensitive resin composition containing a light-shielding agent is preferably used for formation of a black matrix or a black column spacer in a liquid crystal display panel, and formation of the bank for division of the light emitting layer in an organic electroluminescent element.

As mentioned above, the cured film formed using the photosensitive resin composition has little generation|occurrence|production of a gas. Therefore, the bank formed by using the photosensitive resin composition hardly causes damage to the organic light emitting material (light emitting layer) or the electrode with respect to the organic EL device. And, when the bank contains a light-shielding agent, it is easy to prevent internal reflection in the organic EL element or incident light of unnecessary light into the organic EL element.

From the above, the photosensitive resin composition containing the light-shielding agent is particularly preferably used for formation of a bank for partitioning a light emitting layer in an organic EL device.

When using a colorant (E) as a light-shielding agent, it is preferable to use a black pigment or a purple pigment as a light-shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, metal oxides such as silver, complex oxides, metal sulfides, Various pigments are mentioned regardless of organic substances, such as a metal sulfate and a metal carbonate, and an inorganic substance.

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

As carbon black, carbon black to which the process for introducing an acidic group was made is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity according to the definition of Brønsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black may form a salt. The cation which forms a salt with an acidic group will not be specifically limited if it is a range which does not impair the objective of this invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, and ammonium ions, and alkali metal ions and ammonium ions such as sodium ion, potassium ion and lithium ion are preferable.

Among the carbon blacks subjected to the treatment for introducing an acid group described above, from the viewpoint of achieving high resistance of a light-shielding cured film formed using the photosensitive resin composition, a carboxylic acid group, a carboxylic acid base, a sulfonic acid group, and a sulfonic acid group Carbon black having at least one functional group selected from the group consisting of bases is preferable.

The method of introducing an acidic group into carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example.

1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using a sulfite or hydrogen sulfite salt.

2) A method of diazo coupling an organic compound having an amino group and an acid group and carbon black.

3) A method in which an organic compound having a halogen atom and an acid group and carbon black having a hydroxyl group are reacted by Williamson's etherification method.

4) A method of reacting an organic compound having an acidic group protected by a halocarbonyl group and a protecting group with carbon black having a hydroxyl group.

5) A method of performing a Friedel-Crafts reaction on carbon black using an organic compound having an acidic group protected by a halocarbonyl group and a protecting group, followed by deprotection.

Among these methods, method 2) is preferable from the viewpoint of easy and safe introduction of an acidic group. As the organic compound having an amino group and an acidic group used in 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 acid such as sulfanilic acid and aminobenzoic acid such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as it does not impair the object of the present invention. 1-200 mmol are preferable with respect to 100 g of carbon black, and, as for the mole number of the acidic group introduce|transduced into carbon black, 5-100 mmol are more preferable.

The carbon black to which an acidic group has been introduced may be coated with a resin. When using the photosensitive resin composition containing carbon black coated with resin, it is easy to form the light-shielding cured film which is excellent in light-shielding property and insulation and has a low surface reflectance. Moreover, the bad influence with respect to the dielectric constant of the light-shielding cured film formed using the photosensitive resin composition by the coating process with resin in particular does not generate|occur|produce. Examples of resins usable for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphthalate resin, epoxy resin, and alkylbenzene resin, polystyrene, polycarbonate, and polyethylene terephthalate. Phthalate, polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfurpolyphenylenesulfone, polyarylate, poly and thermoplastic resins such as ether ether ketone. It is preferable that the coating amount of resin with respect to carbon black is 1-30 mass % with respect to the sum total of the mass of carbon black and the mass of resin.

Moreover, as a light-shielding agent, a perylene type pigment is also preferable. 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). can In a commercial item, product names K0084 and K0086 by BASF Corporation, Pigment Black 21, 30, 31, 32, 33, 34, etc. can be used preferably as a perylene type pigment.

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 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or an acetyl group.

In formula (e-2), R ^e5 and R ^e6 each independently represent a C1-C7 alkylene group.

In formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom or a C1-C22 alkyl group, and may contain the hetero atom of N, O, S or P. ^{When Re7} and ^Re8 are an alkyl group, linear or branched form may be sufficient as the said alkyl group.

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, Japanese Patent Application Laid-Open Nos. 62-1753 and Japanese Kokai 63 -26784 can be synthesized using the method described in the publication. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is carried out in water or an organic solvent. Then, the target product can be obtained by recrystallizing the obtained preparation in sulfuric acid or recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

In order to disperse the perylene-type pigment favorably in a composition, it is preferable that the average particle diameter of a perylene-type pigment is 10-1000 nm.

In addition, the light-shielding agent may contain a lactam-based pigment. As a lactam pigment, the compound represented by following formula (e-4) is mentioned, for example.

In the formula (e-4), X ^e represents a double bond, and each is independently an E or Z form as a geometric isomer, and R ^e9 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or chlorine An atom, a fluorine atom, a carboxyl group or a sulfo group is represented, R ^e10 each independently represents a hydrogen atom, a methyl group or a phenyl group, and R ^e11 each independently represents a hydrogen atom, a methyl group or a chlorine atom.

The compound represented by a formula (e-4) can be used individually or in combination of 2 or more type.

R ^e9 is preferably bonded to the 6-position of the dihydroindolone ring from the viewpoint of easy preparation of the compound represented by the formula (e-4), and R ^e11 is preferably bonded to the 4-position of the dihydroindolone ring. do. From the same viewpoint, ^Re9 , ^Re10 and ^Re11 are preferably hydrogen atoms.

The compound represented by the formula (e-4) has an EE form, a ZZ form, and an EZ form as geometric isomers, but any single compound of these may be used or a mixture of these geometric isomers may be sufficient.

The compound represented by Formula (e-4) can be manufactured by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624, for example.

In order to disperse|distribute a lactam type pigment favorably in a composition, it is preferable that the average particle diameter of a lactam type pigment is 10-1000 nm.

In addition, fine particles containing a silver tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as a light-shielding agent. The AgSn alloy fine particles may have an AgSn alloy as a main component, and may contain, for example, Ni, Pd, Au or the like as other metal components. As for the average particle diameter of this AgSn alloy microparticles|fine-particles, 1-300 nm is preferable.

When the AgSn alloy is expressed by the 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 chemical stability and blackness can be obtained at the same time is 3≤x≤4 .

Here, if the mass ratio of Ag in the AgSn alloy is obtained in the range of x,

For x=1, Ag/AgSn=0.4762

For x=3, 3 Ag/Ag3Sn=0.7317

For x=4, 4·Ag/Ag4Sn=0.7843

For x=10, 10 Ag/Ag10Sn=0.9008

becomes this

Therefore, this AgSn alloy becomes chemically stable when it contains 47.6 to 90 mass % of Ag, and when it contains 73.17 to 78.43 mass % of Ag, chemical stability and blackness can be effectively obtained with respect to the amount of Ag.

These AgSn alloy fine particles can be produced using a normal fine particle synthesis method. Examples of the method for synthesizing the fine particles include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze drying method, and a hydrothermal synthesis method.

Although AgSn alloy fine particles have high insulating properties, depending on the use of the photosensitive resin composition, the surface may be covered with an insulating film in order to further improve the insulating property. As a material of such an insulating film, a metal oxide or an organic high molecular compound is preferable. As the metal oxide, a metal oxide having insulating properties, for example, silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), etc. are preferably used. . In addition, as the organic polymer compound, a resin having insulating properties, for example, polyimide, polyether, polyacrylate, polyamine compound, and the like are 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 properties 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, the use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable 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 may be used in combination. In addition, the light-shielding agent may contain pigments of colors such as red, blue, green, and yellow together with the above-mentioned black pigments and purple pigments for the purpose of adjusting color tone or the like. The pigment|dye of the other color of a black pigment or a purple pigment can be suitably selected from well-known pigment|dye. For example, as a pigment having a color different from that of a black pigment or a purple pigment, the above various pigments may be used. 15 mass % or less is preferable with respect to the total mass of a light-shielding agent, and, as for the usage-amount of the pigment|dye of other colors than a black pigment or a purple pigment, 10 mass % or less is more preferable.

In order to uniformly disperse the colorant described above in the composition, a dispersant may be further used. As such a dispersing agent, 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. Moreover, gas generation from the cured film resulting from a dispersing agent may occur. Therefore, it is also preferable that the colorant is subjected to a dispersion treatment without using a dispersant.

In addition, the inorganic pigment and the organic pigment may each be used alone or in combination of two or more, but in the case of using them together, it is preferable to use the organic pigment in the range of 10 to 80 parts by mass relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment, , it is more preferable to use in the range of 20-40 mass parts.

In addition, the photosensitive resin composition can use dye other than a pigment as a coloring agent (E). What is necessary is just to select this dye suitably from well-known materials. As the dye applicable to the photosensitive resin composition of the present embodiment, for example, azo dye, metal complex salt azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye, cyanine dye, naphthoquinone dye, quinoneimine dye, A methine dye, a phthalocyanine dye, etc. are mentioned. Moreover, about these dyes, it can be disperse|distributed to an organic solvent etc. by laking (salt formation), and can use this as a coloring agent (E). In addition to these dyes, for example, the dyes described in Japanese Patent Application Laid-Open Nos. 2013-225132, 2014-178477, 2013-137543, 2011-38085, and 2014-197206 can also be preferably used. . These dyes can also be used in combination with the above-mentioned pigments (for example, perylene pigments, lactam pigments, AgSn alloy fine particles, etc.).

The amount of the colorant (E) used in the photosensitive resin composition can be appropriately selected as long as it is a range that does not impair the object of the present invention, and typically 5 to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) to be described later. 70 mass % is preferable, and 25-60 mass % is more preferable.

It is preferable to add a coloring agent (E) to the photosensitive resin composition, after making it into the dispersion liquid disperse|distributed to the appropriate density|concentration in presence or absence of a dispersing agent. In addition, in this specification, with respect to the usage-amount of the above-mentioned coloring agent (E), it can define as a value including the dispersing agent which exists.

<Fluorine-based resin (F)>

The photosensitive resin composition may contain the fluororesin (F) (henceforth, it describes also as "(F) component"). When the photosensitive resin composition contains a fluororesin (F), liquid repellency is provided to the cured film formed using the photosensitive resin composition. For example, when a light emitting layer is formed by a printing method such as an inkjet method in an area partitioned by the bank on a substrate for an organic EL element having a bank formed by using a photosensitive resin composition, the bank is printed with ink. By flicking the , it is possible to prevent adhesion of ink to a bank or mixing of ink with adjacent pixels when ink is injected into an area surrounded by the bank.

Fluorine resin (F) is resin containing a fluorine atom, and if it is resin which can provide liquid repellency to the cured film formed using the photosensitive resin composition, it will not specifically limit. 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 containing no fluorine atom.

As a preferable example of a fluororesin (F), the copolymer which copolymerized at least the monomer which has (f1) an ethylenically unsaturated group and a fluorine atom, and (f2) (meth)acrylic acid is mentioned. When such a fluororesin (F) is used, it is easy to form a cured film excellent in liquid repellency, particularly a bank for an organic EL device excellent in liquid repellency, using the photosensitive resin composition.

((f1) a 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") will not be specifically limited as long as it has an ethylenically unsaturated group and a fluorine atom. Examples of the monomer (f1) include compounds represented by the following formula (f1-1). These (f1) monomers can be used individually or in combination of 2 or more types.

In formula (f1-1), X ¹ and X ² each 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 represent a hydrogen atom , a fluorine atom or a perfluoromethyl group. Rf represents a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond having 2 to 100 carbon atoms, a represents an integer of 0 to 3, b and c are each independently 0 or 1 indicates When Rf is a fluorine-containing alkyl group, 2-20 are preferable, as for the number of carbon atoms, 3-10 are more preferable, and 4-6 are especially preferable. 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 carbon atoms.

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

Further, in the (f1) monomer, it is preferable to have a group represented by -(CF ₂ ) _t F (t=1 to 10). As for t, it is more preferable that it is 1-8, and it is still more preferable that it is 2-6. (f1) When a monomer has said group, it is easy to form the cured film excellent in liquid repellency with the photosensitive resin composition.

<(f2) (meth)acrylic acid>

In order to improve the developability of the photosensitive resin composition, it is preferable that a fluororesin (F) contains the unit derived from (f2) (meth)acrylic acid which is a monomer which has a carboxyl group.

(f2) It is preferable that content of the unit derived from (meth)acrylic acid is 0.1-20 mass % with respect to the mass of a fluororesin (F). When content of the unit derived from (f2) (meth)acrylic acid in a fluororesin (F) is made into the said range, it is easy to obtain the photosensitive resin composition which can form the cured film excellent in developability and liquid repellency. becomes

You may copolymerize other monomers other than said (f1) monomer and (f2) monomer with the fluororesin (F) as needed. Such other monomers include various monomers described below.

((f3) a monomer having an ethylenically unsaturated group and an epoxy group)

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

(f3) as a 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 an epoxy group of an epoxy compound having more than one function and a monomer obtained by reacting with a monomer obtained by reacting a hydroxyl group or a carboxyl group of an acrylic monomer having a hydroxyl group or a carboxyl group in the side chain and an epoxy group of a bifunctional or more functional epoxy compound.

Especially, glycidyl (meth)acrylate is preferable.

These (f3) monomers can be used individually or in combination of 2 or more types.

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

When the fluororesin (F) contains a unit derived from the (f3) monomer, the content of the unit in the fluororesin (F) is preferably 1 to 40 mass% with respect to the mass of the fluororesin (F), and 5 to 15 mass % is more preferable. When content of the unit derived from the (f3) monomer in a fluororesin (F) is made into said range, it becomes easy to obtain the photosensitive resin composition which can form the cured film with favorable liquid repellency.

((f4) a monomer having a structure represented by formula (f4-1))

It is preferable that the fluororesin (F) is a copolymer obtained by copolymerizing a monomer having an ethylenically unsaturated group and a structure represented by the following formula (f4-1) (hereinafter also referred to as “(f4) monomer”). . (f4) By copolymerizing a monomer, it becomes easy to obtain the photosensitive resin composition excellent in developability, and compatibility of the fluororesin (F) and another component in the photosensitive resin composition can be improved.

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

In 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 a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and may be linear or branched. Especially, a C1-C3 alkyl group is preferable and a methyl group is the most preferable. As said substituent, a carboxyl group, a hydroxyl group, a C1-C5 alkoxy group, etc. are mentioned. x represents an integer of 1 or more, the integer of 1-60 is preferable, and the integer of 1-12 is more preferable.

As such a (f4) monomer, the compound etc. which are represented by a following formula (f4-3) are mentioned. These (f4) monomers can be used individually or in combination of 2 or more types.

In formula (f4-3), R ^f4 represents a hydrogen atom or a methyl group. R ^f2 , R ^f3 , and x are the same as in Formulas (f4-1) and (f4-2).

(f4) The content of the unit derived from the monomer is preferably 1 to 40 mass%, more preferably 5 to 25 mass% with respect to the mass of the fluororesin (F). By setting it as said range, there exists a tendency for the compatibility of the developability of the photosensitive resin composition and the fluororesin (F) and another component in the photosensitive resin composition to become favorable, and it is preferable.

((f5) a monomer having a silicon atom)

The fluororesin (F) is preferably a copolymer obtained by copolymerizing a monomer having a silicon atom (hereinafter also referred to as "(f5) monomer"). (f5) The 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 with the photosensitive resin composition can be improved more.

Examples of the (f5) monomer include compounds represented by the following formula (f5-1). These (f5) monomers can be used individually or in combination of 2 or more types.

In formula (f5-1), R ^f5 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. R ^f6 represents an alkylene group or phenylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. R ^f7 and R ^f8 each independently represent an alkyl group or a phenyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. When a plurality of R ^f7 is bonded to Si, the plurality of R ^f7 may be the same or different. In addition, when a plurality of (OR ^f8 ) is bonded to Si, the plurality of (OR ^f8 ) may be the same or different. p is 0 or 1, preferably 1. q is an integer of 1-3, Preferably it is 2 or 3, More preferably, it is 3.

(f5) The content of the unit derived from the monomer is preferably 20 mass % or less, more preferably 10 mass % or less, with respect to the mass of the fluororesin (F). By setting it as said range, compatibility with components other than liquid repellency and the photosensitive resin composition tends to become favorable, and it is preferable.

Various monomers having an ethylenically unsaturated group may be used as other monomers other than the above monomers, and among them, an acrylic monomer is preferable. Preferred examples of the acrylic monomer include 2-hydroxyethyl methacrylate (HEMA), N-hydroxymethyl acrylamide (N-MAA), methyl methacrylate (MAA), cyclohexyl methacrylate (CHMA), isobornyl Methacrylate (IBMA) etc. are mentioned. It is preferable that content of the unit derived from these other monomers in fluororesin (F) is 0-25 mass % with respect to the mass of fluororesin (F).

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

It is preferable that the mass average molecular weights of a fluororesin (F) are 2,000-50,000, More preferably, it is 5,000-20,000. By making the mass average molecular weight of a fluorine-type resin (F) 2,000 or more, the heat resistance and intensity|strength of the cured film formed with the photosensitive resin composition can be improved, and the developability of the photosensitive resin composition can be improved by setting it as 50,000 or less.

The content of the fluorine-based resin (F) in the photosensitive resin composition is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass%, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) to be described later. do. When the photosensitive resin composition contains the fluorine-based resin (F) in such an amount, the sensitivity, developability, and resolution of the photosensitive resin composition are excellent, and it is easy to impart good liquid repellency to a cured film formed using the photosensitive resin composition do.

<Organic solvent (S)>

It is preferable that the photosensitive resin composition contains the organic solvent (S) for the improvement of applicability|paintability, or viscosity adjustment.

Specifically as the organic solvent (S), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl (poly)alkylene glycol monoalkyl ethers such as ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate; (poly)alkylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , other ethers such as diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate, 2-hydroxypropionic acid lactic acid alkyl esters such as ethyl; 2-hydroxy-2-methylpropionate ethyl, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxypropionate ethyl, ethoxyacetic acid Ethyl, ethyl hydroxyacetate, 2-hydroxy-3-methyl butanoate, 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-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N ,N-dimethylacetamide, N,N-dimethylisobutylamide, N,N-diethylacetamide, N,N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imida Nitrogen-containing polar organic solvents, such as zolidinone, pyridine, and N,N,N',N'- tetramethylurea; etc. are mentioned.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers, lactic acid alkyl esters, and other esters described above are preferable. One other ether, the above-mentioned other esters are more preferable. Moreover, it is also preferable that the organic solvent (S) contains the nitrogen-containing polar organic solvent from points, such as solubility of each component, dispersibility of a coloring agent (E). The nitrogen-containing polar organic solvent is preferably N,N,N',N'-tetramethylurea. These solvents can be used individually or in combination of 2 or more types.

Content of the organic solvent (S) is not specifically limited, It sets suitably according to the film thickness of application|coating at the density|concentration which can be apply|coated to a board|substrate etc. It is preferable that it is 5-500 cp, and, as for the viscosity of the photosensitive resin composition, it is more preferable that it is 10-50 cp, It is more preferable that it is 20-30 cp. Moreover, it is preferable that it is 5-100 mass %, and, as for the density|concentration of solid content, it is more preferable that it is 15-50 mass %.

<Other ingredients>

The photosensitive resin composition can contain additives, such as surfactant, an adhesive improving agent, a thermal-polymerization inhibitor, an antifoamer, and a silane coupling agent, as needed. A conventionally well-known thing can be used for any additive.

It is preferable that the photosensitive resin composition contains a silane coupling agent at the point which a shape is favorable and it is easy to form the cured film excellent in adhesiveness with respect to a board|substrate. As the silane coupling agent, a conventionally known coupling agent may be used without any particular limitation.

The surfactant includes compounds such as anionic, cationic, and nonionic, the thermal polymerization inhibitor includes hydroquinone and hydroquinone monoethyl ether, and the defoaming agent includes silicone and fluorine compounds. .

<The preparation method of the photosensitive resin composition>

The photosensitive resin composition demonstrated above can be obtained by mixing each said component uniformly, after mixing predetermined amounts, respectively with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become more uniform.

<< a bank for partitioning a light emitting layer in a cured film and an organic EL device, a substrate for an organic EL device including a bank, and an organic EL device including a bank >>

A cured film is formed by hardening the thin film formed using the photosensitive resin composition demonstrated above by exposure and a heating.

An insulating film is mentioned as a use of a cured film. When the photosensitive resin composition does not contain a coloring agent (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.

Preferred examples of the light-shielding black insulating film include black barrier ribs in a black matrix and black column spacers included in various image display device panels.

Moreover, when the photosensitive resin composition contains chromatic coloring agents (E), such as RGB, a colored cured film can be formed in the area|region partitioned by the black matrix, and a color filter can be manufactured.

For example, the color filter containing the said black matrix and a chromatic cured film as hardened|cured material is used suitably with respect to various display apparatuses.

Moreover, as mentioned above, there is little generation|occurrence|production of a gas in such a cured film. Therefore, the cured film formed using the photosensitive resin composition is used suitably as a bank for division of the light emitting layer in an organic electroluminescent element.

The bank is formed on a substrate for an organic EL device 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. A pixel is formed by dividing the light emitting layer by banks. Here, when the electrode layer or the light emitting layer is contaminated by a gas containing various components generated from the bank, deterioration is accelerated.

However, when the cured film formed 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 durability of the organic EL device is improved. That is, the organic electroluminescent element provided as a bank with the cured film formed using the photosensitive resin composition demonstrated above is excellent in durability.

In addition, the board|substrate provided with the bank formed using the photosensitive resin composition described above is useful as a board|substrate for organic electroluminescent elements. By using such a substrate for an organic EL device, it is possible to manufacture an organic EL device having excellent durability in which deterioration of the electrode layer and the light emitting layer is suppressed.

≪Method for producing cured film≫

As a manufacturing method of a cured film, in the thin film of the photosensitive resin composition, the photopolymerizable monomer (B) is polymerized, and also it hardens|cures by causing the crosslinking reaction of alkali-soluble resin (A) and polyfunctional crosslinking compound (D). It will not specifically limit if it is a method which can form a film|membrane.

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

As a preferable manufacturing method of a cured film,

The process of forming a coating film by apply|coating the photosensitive resin composition;

exposing the coating film;

The method including the process of hardening the exposed coating film is mentioned.

In order to form a cured film using the photosensitive resin composition, the photosensitive resin composition is apply|coated on the board|substrate selected according to the use of a cured film, and a coating film is formed. 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, reverse coater, or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used. .

The apply|coated photosensitive resin composition is dried as needed, and comprises a coating film. The drying method is not particularly limited, for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. on a hot plate, (2) several hours at room temperature A method of leaving it to stand for several days, (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, etc. are mentioned.

Next, the coating film is exposed. Exposure is performed by irradiating active energy rays, such as an ultraviolet-ray and excimer laser light. The exposure may be positionally selective, for example, by a method of exposing through a negative mask. Although the amount of energy to be irradiated varies depending on the composition of the photosensitive resin composition, for example, about 40 to 200 mJ/cm ² is preferable.

When the coating film is positionally exposed to light, it is patterned into a desired shape by developing the exposed film with a developer. The developing method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. The developer is appropriately selected according to the composition of the photosensitive resin composition. As a developing solution, alkaline aqueous solutions, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt, can be used, for example.

Next, the exposed coating film or the patterned coating film after image development is hardened, and a cured film is formed. In this curing, a crosslinking reaction between the alkali-soluble resin (A) and the polyfunctional crosslinkable compound (D) is caused. Therefore, in order to harden, it bakes about the exposed coating film or the patterned coating film after image development.

Although baking temperature is not specifically limited as long as hardening advances favorably, 180-280 degreeC is preferable and 190-260 degreeC is more preferable.

By baking as mentioned above, the cured film of the photosensitive resin composition can be obtained.

«Method for manufacturing a bank for partitioning a light emitting layer in an organic EL device»

The method of manufacturing the bank for partitioning the light emitting layer in the organic EL element is not particularly limited as long as it is a method capable of manufacturing the bank at a predetermined position on the substrate for the organic EL element.

In a preferred way,

A step of forming a coating film on a substrate for an organic EL device by applying the photosensitive resin composition;

a step of positionally selectively exposing a location corresponding to the position of the bank in the coating film;

a process of developing the exposed coating film;

The method including the process of hardening the developed coating film is mentioned.

As a typical example of a board|substrate, the transparent board|substrate provided with the transparent electrode layer (anode) which consists of ITO etc. at the location corresponding to the location where the light emitting layer is formed on one side of a main surface is mentioned.

The bank is formed so as to surround the region where the light emitting layer is formed while being in contact with the end of the transparent electrode layer.

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

By the method described above, it is possible to obtain a substrate having a bank for partitioning the light emitting layer at a predetermined position on the substrate for an organic EL element.

≪Method for manufacturing organic EL device≫

An organic EL device is manufactured using the substrate for the organic EL device provided with the bank described above.

The method includes a step of forming a light emitting layer in a region partitioned by banks in a substrate for an organic EL device.

A transparent electrode layer (anode) made of ITO or the like is exposed in a region partitioned by the banks of the substrate for an organic EL device having a bank.

In a typical method, a hole transport layer is laminated on an electrode layer (anode). Then, an electron transport layer and an electrode layer (cathode) are laminated in this order on the hole transport layer to manufacture an organic EL device. A TFT, a color filter, etc. may be suitably combined in addition as needed.

The method for forming the hole transport layer, the light emitting layer, the electron transport layer, etc. 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 especially preferable as a printing method from the point which there is little loss of the material for layer formation and it is easy to quickly form the layer of a desired film thickness at a predetermined position.

Since the organic EL device manufactured by the above method has a bank with little gas generation, deterioration of the electrode layer or the light emitting layer is suppressed, and thus the durability is excellent.

<Example>

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

[Preparation Example 1]

In 1500 mL four old flasks, 275 g (0.5 mol, epoxy equivalent 292) of an epoxy compound represented by the following formula, 100 mg of 2,6-ditertbutyl-4-methylphenol, and 72 g of acrylic acid were added together with a catalyst, , while blowing air at a rate of 25 mL/min, it was dissolved by heating at 90 to 100 °C.

Next, the solution was heated to 120 ℃ by slowly raising the temperature in a cloudy state to completely dissolve. Here, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate of the structure of the following formula of a colorless and transparent solid state.

Next, 650 g of propylene glycol monomethyl ether acetate was added to and dissolved in 347.4 g (0.5 mol) of the bisphenol fluorene type epoxy acrylate obtained in this way, and then a compound of the following formula (b1)-1 (hereinafter, the compound ( b1)-1) (0.25 mol) was mixed with a catalyst, and the temperature was gradually increased to react at 130° C. for 4 hours.

In addition, compound (b1)-1 is a tetracarboxylic dianhydride represented by the following formula (norbornane-2-spiro-α-cyclopentanone-α′-spiro-2′-novonane-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, reacted at 90° C. for 6 hours, and bisphenol fluorene type epoxy acrylate and acid anhydride (compound (b1) ) -1) to obtain a resin A1, which is a cardo resin produced. Disappearance of the acid anhydride was confirmed by IR spectrum.

[Preparation Example 2]

Except not carrying out the reaction using 30 g of 1,2,3,6-tetrahydrophthalic anhydride, it carried out similarly to Preparation Example 1, and obtained Resin A2 which is cardo resin.

[Preparation Example 3]

In the same manner as in Example 1, except that 3,3',4,4'-biphenyltetracarboxylic dianhydride was used at an equimolar concentration in place of the compound (b1)-1, a cardo resin, Resin A3, was obtained.

[Preparation Example 4]

Except not carrying out the reaction using 30 g of 1,2,3,6-tetrahydrophthalic anhydride, it carried out similarly to Preparation Example 3, and obtained resin A4 which is cardo resin.

[Preparation Example 5]

About Preparation Example 1, except changing the addition amount of 1,2,3,6-tetrahydrophthalic anhydride to 15 g, it carried out similarly to Preparation Example 1, and resin A5 which is cardo resin was obtained.

[Examples 1 to 10, Comparative Example 1, and Comparative Example 2]

In Examples and Comparative Examples, resins A1 to A5 obtained in Preparation Examples 1 to 5 and Resin A6 having the following structure were used as alkali-soluble resin (A) (component (A)). The numerical value in the lower right corner of parentheses in the following formula is the ratio (mass %) of each structural unit in 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 of the following structure was used as the photopolymerization initiator (C) (component (C)).

In Examples and Comparative Examples, as the polyfunctional crosslinkable compound (D), the following D1, D2, and D4 and siloxane polyfunctional epoxy compound D3 (molecular weight: 3400, epoxy equivalent: 147 g/eq, number of epoxy groups in one molecule) : about 23) was used.

The molecular weight of D1 is 737.27, the epoxy equivalent is 184 g/eq, and the number of epoxy groups in one molecule is 4.

The molecular weight of D2 is 381.42, the epoxy equivalent is 127 g/eq, and the number of epoxy groups in 1 molecule is 3.

The molecular weight of D4 is 252.31, the epoxy equivalent is 126 g/eq, and the number of epoxy groups in 1 molecule is 2.

In Examples and Comparative Examples, the following E1 to E3 light-shielding agents were used as the colorant (E) (component (E)).

E1: Lactam pigment

E2: Perylene-based pigment

E3: AgSn pigment

(A) component of the kind and amount shown in Table 1, 7 parts by mass of (B) component, 8 parts by mass of (C) component, 10 parts by mass of (D) component of the kind shown in Table 1, and of the kind shown in Table 1 (E) 45 mass parts of components were mixed uniformly in the organic solvent so that the mass ratio of components other than an organic solvent might be set to 20 mass %, and the photosensitive resin composition of each Example and a comparative example was obtained.

In Comparative Example 1, 40 parts by mass of the component (A) was used without using the polyfunctional crosslinkable compound (D).

In addition, as an organic solvent, the mixed solvent which consists of 60 mass % of propylene glycol monomethyl ether acetate, 20 mass % of 3-methoxybutyl acetate, and 20 mass % of N,N,N',N'- tetramethylurea was used.

<Gas generation evaluation>

After coating the photosensitive resin compositions of each Example and Comparative Example on a glass substrate of 10 cm × 10 cm, the film was 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.

With respect to the exposed coating film, it post-baked at 230 degreeC for 30 minutes, and obtained the cured film whose film thickness is 2 micrometers.

The formed cured film was used as a sample, and the amount of generated gas was evaluated by gas chromatography mass spectrometry (P&T-GC/MS) equipped with a purge & trap sampler (thermal desorption device). Measurement and gas quantification were performed according to the following procedures (i) to (iii).

(i) Gas generation and collection in secondary adsorption tube

1 mg of the cured film was put into the primary trap tube and heated at 230° C. for 10 minutes using a heat desorption device (manufactured by PerkinElmer: TarboMatrixATD) to adsorb the released gas to the secondary trap tube.

(ii) GC/MS analysis

The secondary trap tube was heated at 250° C. for 1 minute, and the released gas was analyzed by GC/MS (manufactured by Agilent Technologies: 7890 B (GC), 5977 AMSD (MS)).

(iii) quantitative analysis

Quantification 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.

Evaluation of 3-5 is interpreted as having little gas generation amount.

Table 1 shows the evaluation results.

5: Value of evaluation value is less than ^1.0E8 .

4: The value of evaluation value is ^1.0E8 or more and less than ^2.5E8 .

3: The value of evaluation value is ^2.5E8 or more and less than ^5.0E8 .

2: The value of evaluation value is ^5.0E8 or more and less than ^1.0E9 .

1: The value of the evaluation value is ^1.0E9 or more.

<Table 1>

According to an example, alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a polyfunctional crosslinking compound (D) are included, and alkali-soluble resin (A) is cardo It can be seen that a cured film formed by using a photosensitive resin composition containing a resin and having an epoxy equivalent of 50 to 350 g/eq of the polyfunctional crosslinkable compound (D) has a small amount of gas generation.

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 instead of a cardo resin as the alkali-soluble resin (A), the photosensitive resin composition It turns out that there is much gas generation amount from the cured film formed using it.

Claims (15)

An alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a polyfunctional crosslinkable compound (D) having a plurality of epoxy groups or oxetanyl groups in one molecule,
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 to 350 g/eq,
The photosensitive resin composition, wherein the polyfunctional crosslinkable compound (D) comprises a siloxane compound having two or more epoxy groups per molecule. The method according to claim 1,
The photosensitive resin composition which further contains a light-shielding agent as a coloring agent (E). The method according to claim 1,
The resin having the cardo skeleton, the following formula (a-1):

(in formula (a-1), X ^a is the following formula (a-2):

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

represents a group represented by , ring A in the formula (a-3) represents an aliphatic ring in which an aromatic ring may be condensed or may have a substituent, R ^a0 is a hydrogen atom or a group represented by -CO-Y ^a -COOH and Y ^a represents a divalent residue excluding acid anhydride groups in dicarboxylic acid anhydride, and Z ^a represents a tetravalent residue excluding two acid anhydride groups in tetracarboxylic dianhydride. In addition, in formula (a-1), m1 represents the integer of 0-20.)
The resin represented by the photosensitive resin composition. 4. The method according to claim 3,
The tetracarboxylic dianhydride has the following formula (a-4):

(In formula (a-4), R ^a4 , R ^a5 and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 is 0 to 12 represents the integer of .)
Represented, the photosensitive resin composition of the compound. 5. The method according to any one of claims 1 to 4,
The photosensitive resin composition whose ratio of content [g] of the said alkali-soluble resin (A) and content [g] of the said polyfunctional crosslinking|crosslinked compound (D) is the range of 15:1-0.5:1. 5. The method according to any one of claims 1 to 4,
A photosensitive resin composition used for forming a bank for partitioning a light emitting layer in an organic EL device. The cured film formed by hardening|curing the photosensitive resin composition in any one of Claims 1-4. A bank for partitioning a light emitting layer in an organic EL device, which is formed by curing the photosensitive resin composition according to claim 6 . A substrate for an organic EL device comprising the bank according to claim 8 . An organic EL device comprising the bank according to claim 8 . The process of forming a coating film by apply|coating the photosensitive resin composition in any one of Claims 1-4;
exposing the coating film; and
The manufacturing method of the cured film including the process of hardening the said coating film which was exposed. 12. The method of claim 11,
In the exposing step, the coating film is positionally exposed,
The manufacturing method of the cured film which further includes the process of developing the said coating film exposed between the said process of exposing and the said hardening process. A method for manufacturing a bank for partitioning a light emitting layer of an organic EL device on a substrate, the method comprising:
The process of forming a coating film on the said board|substrate by apply|coating the photosensitive resin composition of Claim 6;
a step of positionally selectively exposing a portion of the coating film corresponding to the position of the bank;
developing the exposed coating film; and
and curing the developed coating film. 10. A method of manufacturing an organic EL device, comprising the step of forming a light emitting layer in a region partitioned by the bank in the substrate for the organic EL device according to claim 9. delete