KR20200035870A - Photosensitive resin composition, method for forming patterned cured film, and cured film - Google Patents

Abstract

The present invention relates to a photosensitive resin composition excellent in patterning properties, a production method of a cured film, and a cured product. The photosensitive resin composition comprises an alkali-soluble resin (A), a cross-linking agent (B), and a photopolymerization initiator (C). In addition, the photosensitive resin composition comprises a mono-functional (meth)acrylic monomer (B1) having a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have the substituent as the cross-linking agent (B).

Description

Photosensitive resin composition, manufacturing method of patterned cured film and cured film {PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR FORMING PATTERNED CURED FILM, AND CURED FILM}

The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, and a cured film.

Since a cured film patterned in a predetermined shape can be easily formed by a photolithographic method, a photosensitive resin composition containing an alkali-soluble resin is, for example, a display device such as a liquid crystal display, a semiconductor device, or other fields. Widely used in.

In the photosensitive composition, a photopolymerization initiator contained as part of the component generates radicals by exposure. The photosensitive composition is cured by polymerizing the polymerizable compound contained in this radical photosensitive composition. Further, in the photosensitive resin composition, a polymerizable compound is polymerized with radicals generated by such a photopolymerization initiator, while a crosslinking agent component is blended for the purpose of increasing the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition. . As the crosslinking agent component, among the monomers having an ethylenically unsaturated group for the purpose described above, polyfunctional, in particular, dipentaerythritol penta and pentaacrylates or more (meth) acrylate monomers, such as hexaacrylate, have been used.

Recently, from the viewpoint of improving productivity, a highly sensitive photosensitive resin composition capable of forming a pattern with a low exposure amount is desired. On the other hand, in the case of forming a cured film patterned in a complicated shape, in a film made of a photosensitive resin composition that is an object of exposure, there is a case where an area that does not transmit exposure light triggered for curing the photosensitive resin composition increases. . In this case, in the photosensitive resin composition having the composition as described above, it is easy to cause defects in which a portion that is not sufficiently cured after exposure occurs. In addition, the application of photosensitive resin compositions to the sun to obtain a cured film of a relatively thick film having a thickness of several tens of µm or more has been widely studied. However, even in the case of forming a cured film of such a thick film, the exposure light does not sufficiently reach the distal side, that is, generally near the contact surface of the substrate and the photosensitive resin layer, than the light source in the film made of the photosensitive resin composition. No, it is easy to cause defects in which a portion with insufficient curing occurs in the cured film. In addition, in the aspect in which the photosensitive resin composition contains a colorant, the problem of insufficient curing is formed in the cured film by absorption of exposure light by the colorant is remarkable.

In Patent Document 1, a photosensitive resin composition having a specific composition has been proposed for the purpose of satisfactorily curing a region in which the activation energy in the photosensitive resin composition does not directly contact with a low exposure amount. In Patent Document 1, specifically, a monofunctional (meth) acrylic monomer having an aromatic group (A) and a compound (B) having at least one polymerizable carbon-carbon double bond on a molecule other than the component (A) on average , (C) A curable composition containing a photopolymerization initiator has been proposed. As the component (A), specifically, ethoxylated o-phenylphenylacrylate or the like is used, and as the component (B), an acrylic acid ester polymer or the like is specifically used.

Japan Special 2014-51618

However, even in the curable composition as described in Patent Literature 1, there may be cases in which it is not possible to sufficiently satisfy the demand that the problem of insufficient curing is formed in the cured film. Moreover, even if it was possible to suppress the formation of an insufficient part of curing, in this case, the rectangularity (taperability) of the formed line pattern was improved to some extent, while the linearity (reproducibility) and resolution of the line pattern were: Further improvement is desired. For this reason, a photosensitive resin composition which is more excellent in sensitivity is required.

The present invention has been made in view of the problems of the prior art, and provides a photosensitive resin composition having high sensitivity, excellent patterning characteristics such as good line width stability, resolution and rectangularity, a method for manufacturing a patterned cured film using the same, and provision of a cured film The purpose.

The present inventors have a photosensitive resin composition containing a mixture of monofunctional (meth) acrylate compounds having a specific structure, so that the sensitivity of the photosensitive resin composition is high. Good curing proceeds even at a place where the active energy rays forming the film are difficult to directly contact, the pattern has good rectangularity (taperability), and the pattern has good linearity (reproducibility) at high resolution and can improve patterning properties. It has been found that the present invention has been completed. That is, the present invention is as follows.

The first aspect of the present invention,

A photosensitive resin composition comprising an alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C),

It is a photosensitive resin composition containing the monofunctional (meth) acrylate monomer (B1) which has the biphenyl skeleton which may have a substituent as the crosslinking agent (B), or the terphenyl skeleton which may have a substituent.

In the second aspect of the present invention, the photosensitive resin composition according to the first aspect is coated on a substrate to form a photosensitive resin layer, the photosensitive resin layer is selectively exposed selectively, and the exposed photosensitive resin layer is exposed. It is a method of manufacturing a patterned cured film comprising developing with a developer.

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

ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the photosensitive resin composition excellent in patterning characteristics with high sensitivity, good line width stability, resolution, and rectangular property, the manufacturing method of the patterned cured film using this, and the cured film.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to any of the following embodiments, and can be carried out by appropriate changes within the scope of the object of the present invention.

≪Photosensitive resin composition≫

The photosensitive resin composition contains an alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C). The photosensitive resin composition contains, as the crosslinking agent (B), a monofunctional (meth) acrylate monomer (B1) having a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent.

Hereinafter, the components contained in the photosensitive resin composition will be described in order.

<Alkali-soluble resin (A)>

The photosensitive resin composition contains an alkali-soluble resin (A).

Here, in this specification, (A) alkali-soluble resin means the resin provided with the functional group (for example, phenolic hydroxyl group, carboxyl group, sulfonic acid group, etc.) which has alkali solubility in a molecule | numerator.

The type of the alkali-soluble resin (A) is not particularly limited, and various alkali-soluble resins conventionally blended with the photosensitive resin composition can be used.

Hereinafter, resins (A1) having a cardo structure, acrylic resins (A2), and novolac resins (A3) will be described as suitable specific examples of the alkali-soluble resin (A).

[Resin (A1) having a cardo structure]

The photosensitive resin composition may contain, as the alkali-soluble resin (A), a resin (A1) having a cardo structure (hereinafter also referred to as “cardo resin (A1)”).

As the cardo resin (A1), a resin having a desired alkali solubility having a cardo skeleton in its structure can be used. The cardo skeleton refers to a skeleton in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. Moreover, the 2nd cyclic structure and the 3rd cyclic structure may be the same structure, or may be different structures.

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

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

(In formula (a-1), X ^a represents a group represented by the following formula (a-2). M1 represents an integer of 0 or more and 20 or less.)

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

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

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 having 1 to 6 carbon atoms is preferable. Groups are particularly preferred, ethane-1,2-diyl group, propane-1,2-diyl group and propane 1,3-diyl group are most preferred.

About ring A in Formula (a-3), monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane etc. are mentioned as an aliphatic ring.

Specifically, monocycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are mentioned.

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

The following group is mentioned as a suitable example of a divalent group represented by Formula (a-3).

Formula (a-1) 2 a group of X ^a is, by reacting a diol compound represented by the following formula (a-2a) as the tetracarboxylic acid dianhydride to give a residue Z ^a, (A1) acid is also incorporated into the resin .

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 and m2 are as described for formula (a-2). About ring A in Formula (a-2a), it is as having demonstrated about Formula (a-3).

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

First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with a group represented by -R ^a3 -OH according to a conventional method, if necessary, and then epichlorohich. Glycidylation using chin and the like gives an epoxy compound represented by the following formula (a-2c).

Then, the diol compound represented by formula (a-2a) is obtained by reacting the epoxy compound represented by formula (a-2c) with acrylic acid or methacrylic acid.

In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 and m2 are as described for formula (a-2). About ring A in Formula (a-2b) and Formula (a-2c), it is as having demonstrated about Formula (a-3).

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

The following diol compound is mentioned as a suitable 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 a residue excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendmethylene anhydride tetrahydrophthalic acid, chlorendic anhydride, methyltetrahydro phthalic anhydride, And glutaric anhydride.

Moreover, in said Formula (a-1), Z ^a represents the residue which remove | excluding two acid anhydride groups from tetracarboxylic acid anhydride. Examples of the tetracarboxylic acid anhydride include tetracarboxylic acid anhydride represented by the following formula (a-4), pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, and biphenyl ether tetracarboxylic acid anhydride. And the like.

Moreover, in said Formula (a-1), m1 represents the integer of 0 or more and 20 or less.

(In formula (a-4), R ^a4 , R ^a5 and R ^a6 each independently represent one kind 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 or more. Represents an integer of 12 or less.)

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

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

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

It is preferable that the plurality of R ^a4 in the formula (a-4) is the same group in that it is easy to prepare a high-purity tetracarboxylic acid anhydride.

M3 in Formula (a-4) represents the integer of 0 or more and 12 or less. Purification of tetracarboxylic acid anhydride can be facilitated by setting the value of m3 to 12 or less.

From the viewpoint of easy purification of tetracarboxylic acid anhydride, the upper limit of m3 is preferably 5, and more preferably 3.

In view of the chemical stability of the tetracarboxylic acid 2 anhydride, the lower limit of m3 is preferably 1, and more preferably 2.

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

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

Since R ^a5 and R ^a6 are easy to purify tetracarboxylic acid anhydrides, hydrogen atoms or carbon atoms 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably) Is preferably 1 to 4 or less, particularly preferably 1 to 3 or less), and is preferably a hydrogen atom or a methyl group.

As the tetracarboxylic acid 2 anhydride represented by the formula (a-4), for example, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 "-norbornane-5,5" , 6,6 "-tetracarboxylic acid anhydride (alias" norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2 "-norbornane-5,5", 6,6 "- Tetracarboxylic acid 2 anhydride ”), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnorbornane) -5,5 ", 6,6" -tetracarboxylic acid 2 Anhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid 2 anhydride (alias" norbornane-2 -Spiro-2'-cyclohexanone-6'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid 2 anhydride"), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2 "-(methylnorbornane) -5,5", 6,6 "-tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α-cyclopropanone-α ' -Spiro-2 "-nor Renan-5,5 ", 6,6" -tetracarboxylic acid anhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2 "-norbornane-5,5", 6, 6 "-tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2" -norbornane-5,5 ", 6,6" -tetracarboxylic acid 2 anhydride, nord Bornan-2-spiro-α-cyclooctanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α- Cyclononanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro- 2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α-cycloundecanon-α'-spiro-2" -norbornane-5, 5 ", 6,6" -tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetra Carboxylic acid 2 anhydride, norbornane-2- Fatigue-α-cyclotridecanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α-cyclotetradecanone -α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid anhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2" -Norbornane 5,5 ", 6,6" -tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'-spiro-2 "-norbornane-5, 5 ", 6,6" -tetracarboxylic acid 2 anhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α'-spiro-2 "-norbornane-5,5", 6,6 "-Tetracarboxylic dianhydride, etc. are mentioned.

The weight average molecular weight of the cardo resin (A1) is preferably 1000 or more and 40000 or less, and more preferably 2000 or more and 30000 or less. By setting it as the said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

[Acrylic resin (A2)]

As the alkali-soluble resin (A), an acrylic resin (A2) can also be preferably used. In the case of using the acrylic resin (A2), various properties of the photosensitive resin composition can be easily adjusted by appropriately adjusting the type of the monomer, the proportion of the structural unit, and the like.

As the acrylic resin (A2), a resin containing a structural unit derived from (meth) acrylic acid and / or other monomers such as (meth) acrylic acid ester can be used. (Meta) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester is a compound represented by the following formula (a-5) and is not particularly limited as long as it does not impair the object of the present invention.

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

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 halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanate group , Isocyanate group, thiocyanate group, isothiocyanate group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, ah Real group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkylthio ether group, aryl ether Group, arylthioether group, amino group (-NH ₂ , -NHR, -NRR ': R and R' each independently represents a hydrocarbon group) and the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Moreover, the hydrocarbon group contained in the said substituent may be either linear, branched or cyclic.

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

When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups are 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-pen Tyl 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, iso And a decyl group.

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

It is also preferable that the compound represented by Formula (a-5) is an epoxy group-containing unsaturated compound having an epoxy group in R ^a8 .

Suitable examples of the epoxy group-containing unsaturated compound represented by formula (a-5) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. , (Meth) acrylic acid epoxyalkyl esters such as 6,7-epoxyheptyl (meth) acrylate; α-alkyl acrylic acid epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, and α-ethyl acrylate 6,7-epoxyheptyl; And the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferred from the viewpoint of copolymerization reactivity and strength of the resin after curing. Do. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

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

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

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; Anhydrides of these dicarboxylic acids; And the like.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

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

Vinyl esters include vinyl butylate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, And vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

Examples of styrenes include styrene; Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene , Alkyl styrene such as acetoxy methyl styrene; Alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodinestyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Halostyrenes such as styrene and 4-fluoro-3-trifluoromethylstyrene; And the like.

The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from another monomer in the (A3) acrylic resin is not particularly limited within a range that does not impair the object of the present invention. (A3) In the acrylic resin, the amount of the structural unit derived from (meth) acrylic acid is preferably 5 wt% or more and 50 wt% or less, more preferably 10 wt% or more and 30 wt% or less, based on the weight of the acrylic resin. Do.

The weight average molecular weight of the acrylic resin (A2) is preferably 2000 or more and 50000 or less, and more preferably 5000 or more and 30000 or less. By setting it as the said range, there exists a tendency for the balance of the film forming ability of the photosensitive resin composition and developability after exposure to be easy to be balanced.

[Novolak Resin (A3)]

The alkali-soluble resin (A) may contain a novolac resin (A3). When the alkali-soluble resin (A) contains the novolac resin (A3), it is easy to form a cured film having good heat resistance that is difficult to deform by heating.

As the novolac resin (A3), various novolac resins conventionally blended with the photosensitive resin composition can be used. The novolac resin (A3) is preferably a novolac resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and an aldehyde under an acid catalyst.

(Phenols)

Examples of the phenols used when producing the novolac resin (A3) include, for example, phenol; cresols such as o-cresol, m-cresol, and p-cresol; Xenol such as 2,3-xyllenol, 2,4-xylenol, 2,5-xylenol, 2,6-xyllenol, 3,4-xylenol, 3,5-xylenol Silenols; ethyl phenols such as o-ethyl phenol, m-ethyl phenol, and p-ethyl phenol; Alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglysinol; Alkyl polyhydric phenols such as alkyl resorcin, alkyl catechol, and alkyl hydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol; β-naphthol; Hydroxydiphenyl; And bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferably used in combination. In this case, various properties such as heat resistance of the cured film formed using the photosensitive resin composition can be adjusted by adjusting the mixing ratio of both.

Although the blending ratio of m-cresol and p-cresol is not particularly limited, the molar ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol at a ratio in this range, it is easy to obtain a photosensitive resin composition capable of forming a cured film having excellent heat resistance.

Also, novolac resins prepared by using m-cresol and 2,3,5-trimethylphenol in combination are also preferred. When using such a novolac resin, it is particularly easy to obtain a photosensitive resin composition capable of forming a cured film that is difficult to excessively flow by heating during post-baking.

Although the mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, the molar ratio of m-cresol / 2,3,5-trimethylphenol is preferably 70/30 or more and 95/5 or less.

(Aldehydes)

Examples of the aldehydes used when producing the novolac resin (A3) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like. These aldehydes may be used alone or in combination of two or more.

(Acid catalyst)

Examples of the acid catalyst used when producing the novolac resin (A3) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and phosphorous acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and paratoluene sulfonic acid; And metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular Weight)

The weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") in terms of polystyrene of the novolac resin (A3) is a lower limit in terms of resistance to flow due to heating of the cured film formed using the photosensitive resin composition. As is preferred, 2000 is preferred, 5000 is more preferred, 10000 is particularly preferred, 15000 is more preferred, 20000 is most preferred, 50000 is preferred as the upper limit, 45000 is more preferred, 40000 is more preferred, and 35000 is preferred. This is most preferred.

As the novolac resin (A3), at least two resins having different weight average molecular weights in terms of polystyrene may be used in combination. By using resins having different weight average molecular weights in large and small combinations, the developability of the photosensitive resin composition and the heat resistance of the cured film formed using the photosensitive resin composition can be balanced.

The content of the alkali-soluble resin (A) is preferably 30% by weight or more and 90% by weight or less, more preferably 40% by weight or more and 80% by weight or less with respect to the total weight of the solid content of the photosensitive resin composition. By setting it as the said range, it is easy to obtain the photosensitive resin composition excellent in developability.

<(B) crosslinking agent>

(Monofunctional (meth) acrylic monomer (B1))

The photosensitive resin composition contains a crosslinking agent (B), but as the crosslinking agent (B), a monofunctional (meth) acrylic monomer (B1) having a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent is used. Includes. Moreover, "(meth) acrylic monomer" is an acryloyl group and / or methacryloyl group monomer which can be derived from (meth) acrylic acid.

The compound of the following formula is mentioned as a specific example of a monofunctional (meth) acrylic monomer (B1).

In the formula, R ^x is a hydrogen atom or a methyl group. BP is a biphenyl group which may have a substituent, and specific skeleton is 1,1'-biphenyl-4-yl group, 1,1'-biphenyl-3-yl group or 1,1'-biphenyl-2-yl group , Preferably 1,1'-biphenyl-2-yl group or 1,1'-biphenyl-4-yl group. TP is a terphenyl group which may have a substituent, and a specific skeleton is represented by the following formula:

It is any one of the groups represented by.

As the monofunctional (meth) acrylic monomer (B1), a monofunctional (meth) acrylic monomer (B1a) having a biphenyl skeleton which may have a substituent is particularly preferable.

In the monofunctional (meth) acrylic monomer (B1), as the substituent which the biphenyl skeleton and the terphenyl skeleton may have, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon And an alkoxycarbonyl group having 2 to 12 atoms, an acyl group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, or a nitro group.

As a monofunctional (meth) acrylic monomer (B1a), the compound represented by following formula (B1-1) is mentioned preferably.

CH ₂ = CR ^b1 -CO- (OR ^b2- ) _t1 -X ^b1 -BP ... (B1-1)

(In formula (B1-1), R ^b1 is a hydrogen atom or a methyl group, R ^b2 is an alkylene group having 1 to 4 carbon atoms, BP is a biphenyl group which may have a substituent, and t1 is 0 to 10 And when t1 is 0, X ^b1 is -O- or -NH-, and when t1 is an integer of 1 to 10, X ^b1 is a single bond, -O-, -NH-, -O-CO A linking group selected from the group consisting of-*, -NH-CO- *, -O-CO-O- and -NH-CO-O- *. It is a joining hand.)

The substituent which the biphenyl group may have is the same as the substituent exemplified as described above for the substituent which the biphenyl skeleton and the terphenyl skeleton may have.

The number of carbon atoms in the alkylene group as R ^b2 is 1 or more and 4 or less, and 2 or 3 is preferable. As said alkylene group, a linear or branched alkylene group, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and butane-1,2-diyl group, is mentioned, for example. Among these, ethylene group, trimethylene group and propylene group are preferable.

t1 is preferably 0, 1 or 2.

The compound represented by the formula (B1-1) is not particularly limited. The following compound can be illustrated as a suitable example of the compound represented by Formula (B1-1).

As the compound represented by the formula (B1-1), B1-1-a, B1-1-c, B1-1-e, B1-1-f, B1-1-i, B1-1-m Preferred, B1-1-a and B1-1-c are particularly preferred.

(Polyfunctional (meth) acrylic monomer (B2))

The photosensitive resin composition may contain a crosslinking agent (B) other than the monofunctional (meth) acrylic monomer (B1) described above. As crosslinking agent (B) other than monofunctional (meth) acrylic monomer (B1), polyfunctional (meth) acrylic monomer (B2) is mentioned, for example.

As a polyfunctional (meth) acrylic monomer (B2), polyfunctional (meth) acrylate represented by following formula (B2-1) is mentioned preferably, for example.

(In the formula (B2-1), R ^b3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b4 is a t2 hydroxyl group among m hydroxy groups of the polyhydric alcohol R ^b5 (OH) _m . T2 is a residue provided for the ester bond in 1), m and t2 are each independently an integer of 2 or more and 20 or less, and m is t2 or more.)

As a specific example of the polyfunctional (meth) acrylic monomer represented by Formula (B2-1), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( Meta) acrylate, tetramethylene 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-hexaglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, Propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triac Rate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, capro Lactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth)) Acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth B) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, epichlorohi The denatured hexahydrophthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate, trimethylhexamethylene diisocyanate, or 2-hydroxyethyl (meth) acrylate reactant with hexamethylene diisocyanate), neopentyl glycol di (meth) acrylate, hydroxypibaric acid, neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol Di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide Trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, alkoxy (Meth) such as modified trimethylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate and ditrimethylolpropanetetra (meth) acrylate And polyfunctional monomers such as acrylic ester methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth) acrylamide, triacrylic formal, and the like. These polyfunctional monomers can be used alone or in combination of two or more.

Among the specific examples of the polyfunctional (meth) acrylate monomer represented by the formula (B2-1) above, the three-functionality in that the photosensitive resin composition tends to increase adhesion to the substrate and strength after curing of the photosensitive resin composition. The above polyfunctional monomer is preferable, the polyfunctional monomer having 4 or more functionalities is more preferable, and the polyfunctional monomer having 5 or more functionalities is more preferable. In particular, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and mixtures thereof are preferable.

(B) The content of the crosslinking agent in the photosensitive resin composition is preferably 10 wt% or more and 60 wt% or less, more preferably 15 wt% or more and 50 wt% or less, based on the total weight of the solid content of the photosensitive resin composition. By setting it as the said range, there exists a tendency for balance of sensitivity, developability, and resolution to be easy to be balanced.

In addition, the content of the monofunctional (meth) acrylic monomer (B1) relative to the total weight of the crosslinking agent (B) is 1% by weight or more and 100% by weight or less, and 3% by weight or more and 70% by weight or less of the entirety of the component (B) Is preferable, and 5% or more and 50% or less is more preferable. Because the content of the (meth) acrylic monomer (B1) is within the above range, curing of the portion where active energy does not directly contact is promoted during position-selective exposure of the photosensitive resin composition, and thus a thick film, specifically, for example Also, in an aspect in which a cured film having a thickness of 5 µm or more and 50 µm or less is formed, curing can proceed sufficiently even in the vicinity of the substrate side distal from the exposure side.

In a more preferred embodiment, the (B) crosslinking agent is based on the total weight of the (B) crosslinking agent, wherein the monofunctional (meth) acrylic monomer (B1) is 1 wt% or more and 99 wt% or less, and the polyfunctional (meth) acrylic monomer ( B2) preferably contains 1% by weight or more and 99% by weight or less, and 3% by weight or more and 50% by weight or less of the monofunctional (meth) acrylic monomer (B1), and 50 of the polyfunctional (meth) acrylic monomer (B2). It is preferable to contain more than 97% by weight, and in this case, even in the aspect of forming the coated film of the thick film as described above by the photosensitive resin composition, the coated film is fully cured as described above. For this reason, it is easy to make the taper angle of the patterned cured film formed through position-selective exposure and development into a good angle close to a vertical.

<Photopolymerization initiator (C)>

The photosensitive resin composition further contains a photopolymerization initiator (C).

It does not specifically limit as a photoinitiator (C), A conventionally well-known photoinitiator can be used.

Specifically as the photopolymerization initiator (C), for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- 1-one, O-acetyl-1-6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime, (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, ethanone, 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-carbazol-3-yl], 2,4,6-trimethylbenzoyldiphenylphosphine Seed, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, o-benzoyl Methyl benzoate, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mer Captobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzo Phenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxy Benzophenone, benzyl, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p- Dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert- Butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, dibenzosveron, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acrididi Neil) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (triclo Romethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2) -Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (triclo Romethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy Phenyl) -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-bro Mo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, etc. You can. These photoinitiators can be used individually or in combination of 2 or more types.

As the photopolymerization initiator (C), it is also preferable to use an oxime-based compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups,

n1 is an integer of 0 or more and 4 or less,

n2 is 0 or 1,

R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent,

R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the formula (c1), R ^c1 is not particularly limited as long as it does not impair the object of the present invention, and is suitably selected from various organic groups. Suitable 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, a phenyl group which may have a substituent, and a phenoxy group which may have a substituent. Timing, 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, naph which may have a substituent Thoxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, amino group , An amino group substituted with an organic group of 1 or 2, morpholine-1-yl group, and piperazin-1-yl group, halogen, nitro group and cyano group And the like. When n1 is an integer of 2 or more and 4 or less, R ^c1 may be the same or different. Moreover, the number of carbon atoms of the substituent which the substituent further has is not included in the number of carbon atoms of the substituent.

When R ^c1 is an alkyl group, 1 to 20 carbon atoms is preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^c1 is an alkyl group, it may be linear or branched. Specific examples when R ^c1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and iso Pentyl 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, and n-decyl groups and isodecyl groups. Moreover, when R ^c1 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R ^c1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^c1 is an alkoxy group, it may be linear or branched. As a specific example when R ^c1 is an alkoxy group, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy Period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-oc And tiloxy groups, tert-octyloxy groups, n-nonyloxy groups, isononyloxy groups, n-decyloxy groups, and isodecyloxy groups. Moreover, when R ^c1 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group and meth And oxypropyloxy groups.

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 is preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, and n-hexa Noyl 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, and n-pentadecanoyl groups and n-hexadecanoyl groups. Specific examples when R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpro Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group and n-hexadecanoyloxy group.

When R ^c1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. As a specific example when R ^c1 is an alkoxycarbonyl group, 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-heptyloxycarbonyl 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 is preferable, and 7 to 10 carbon atoms are more preferable. Moreover, when R ^c1 is a naphthylalkyl group, 11 or more and 20 or less carbon atoms are preferable, and 11 or 14 or less carbon atoms are more preferable. As a specific example when R ^c1 is a phenylalkyl group, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group are mentioned. Specific examples when R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or is a heterocyclyl group condensed between these monocyclic groups or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed to be up to 3 in number. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, And phthalazine, synnoline, 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 1 or 2 organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms, Saturated aliphatic acyl 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 or less which may have a substituent, a naphthyl group which may have a substituent, or a substituent Naphthyl group, a naphthyl alkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. Specific examples of these suitable organic ^groups are the same as R ^c1 . As a specific example of the amino group substituted by the organic group of 1 or 2, methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group, etc. Can be lifted.

As a substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a number of carbon atoms A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, And dialkylamino groups having an alkyl group of 1 to 6 carbon atoms, morpholine-1-yl group, piperazin-1-yl group, halogen, nitro group and cyano group. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^c1 further has a substituent, the number of the substituents is not limited within a range not impairing the object of the present invention, but 1 to 4 is preferred. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c1 , chemically stable, low steric hindrance, easy synthesis of oxime ester compounds, and the like, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and carbon A group selected from the group consisting of saturated aliphatic acyl groups having 2 to 7 atoms is preferable, alkyl having 1 to 6 carbon atoms is more preferable, and methyl group is particularly preferable.

R ^c1 is a position bonded to the phenyl group for the phenyl group to the R ^c1 bond, the position of the coupling hand of the main skeleton of the phenyl group and the oxime ester compound in the case of 2 up on the location of, and a methyl group No. 1, 4th or 5 The stomach is preferred, and the fifth is more preferred. Moreover, n1 is preferably an integer of 0 or more and 3 or less, an integer of 0 or more and 2 or less is more preferable, and 0 or 1 is particularly preferable.

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

In R ^c2 , the substituent group of the phenyl group or carbazolyl group is not particularly limited as long as it does not impair the object of the present invention. Examples of suitable substituents which the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms , A cycloalkoxy 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, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms , A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent , A phenyl alkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, A naphthoyl group which may have ventilation, a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms or less, which may have a substituent, or a substituent Heterocyclyl groups, heterocyclylcarbonyl groups which may have a substituent, amino groups, amino groups substituted with 1 or 2 organic groups, morpholine-1-yl groups, and piperazin-1-yl groups, halogens, nitro groups, cyano groups, etc. Can be lifted.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a number of carbon atoms. A saturated aliphatic acyl group having 2 or more and 20 or less, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, or a substituent A phenylalkyl group having 7 to 20 carbon atoms or less, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, or 11 to 20 carbon atoms which may have a substituent A naphthyl alkyl group, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. 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.

Regarding specific examples of the substituent which the phenyl group or 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 by the organic group of 1 or 2 are the same as Rc1.

In R ^c2 , examples of the substituent when a phenyl group, a naphthyl group, and a heterocyclyl group further include a substituent included in a substituent having a phenyl group or a carbazolyl group include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazin-1-yl; halogen; Nitro group; And cyano groups. When a phenyl group, a naphthyl group, and a heterocyclyl group included in a substituent having a phenyl group or a carbazolyl group further has a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but is 1 or more 4 or less is preferred. When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

In R ^c2 , the group represented by the following formula (c2) or (c3) is preferable, and the group represented by the following formula (c2) is more preferable from the viewpoint of easy to obtain a photopolymerization initiator having excellent sensitivity, and the following formula (c2) As the group represented by), a group in which A is S is particularly preferable.

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

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

When R ^c4 in the formula (c2) is an organic group, it can be selected from various organic groups within a range that does not impair the object of the present invention. A suitable example in the case where R ^c4 in formula (c2) is an organic group includes an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazin-1-yl; halogen; Nitro group; And cyano groups.

Among R ^c4 , a 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Nitro groups are preferred, and benzoyl groups; Naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.

Moreover, in Formula (c2), n3 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. if n3 is 1, the binding position of R ^c4 are for the combined hand a phenyl group that is R ^c4 bond with oxygen atom or a sulfur atom, it is preferred that the para great.

R ^c5 in the formula (c3) can be selected from various organic groups within a range that does not impair the object of the present invention. Suitable 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, and an alkoxy group having 2 to 20 carbon atoms. A carbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms or less which may have a substituent, 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 heterocyclyl group which may have a substituent, and a substituent And heterocyclylcarbonyl groups.

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

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

As a substituent in the case where a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, Alkoxy group, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, alkyl group having 1 to 6 carbon atoms And monoalkylamino groups having, dialkylamino groups having an alkyl group having 1 to 6 carbon atoms, morpholine-1-yl group, piperazin-1-yl group, halogen, nitro group and cyano group. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 further has a substituent, the number of the substituents is not limited to the extent that does not impair the object of the present invention, but is 1 or more 4 The following are preferred. When a phenyl group, a naphthyl group, and a heterocyclyl group included 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.

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

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

(R ^c7 is a hydrogen atom, a nitro group, or a monovalent organic group, R ^c8 and R ^c9 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^c8 and R ^c9 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, n4 is an integer of 0 or more and 4 or less, and n5 is 0 or 1.)

Here, as the oxime compound for preparing the oxime ester compound of formula (c4), a compound represented by the formula (c5) below is suitable.

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 and n5 are the same as 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 a 6-membered aromatic ring bonded to a group represented _by- (CO) _n5 -on the fluorene ring in formula (c4). In the formula (c4), the binding position of R ^{c7 to} the fluorene ring is not particularly limited. In, that it is the synthesis is easy of the compound of formula (c4), when a compound represented by formula (c4) having one or more of R ^c7, preferably one or more 1, R ^c7 is to combine over two of the fluorene ring Do. When R ^c7 is plural, plural 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 suitably selected from various organic groups. Suitable 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, a phenyl group which may have a substituent, and phenoxy which may have a substituent. Timing, 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, naph which may have a substituent Thoxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, substituent Heterocyclylcarbonyl group optionally having, an amino group substituted with an organic group of 1 or 2, morpholine-1-yl group and piperazine-1 -Diary and the like.

When R ^c7 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when R ^c7 is an alkyl group, it may be linear or branched. Specific examples when R ^c7 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and iso Pentyl 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, and n-decyl groups and isodecyl groups. Moreover, when R ^c7 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R ^c7 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when R ^c7 is an alkoxy group, it may be linear or branched. As a specific example when R ^c7 is an alkoxy group, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy Period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-oc And tiloxy groups, tert-octyloxy groups, n-nonyloxy groups, isononyloxy groups, n-decyloxy groups, and isodecyloxy groups. Moreover, when R ^c7 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group and meth And oxypropyloxy groups.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. 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 cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c7 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, and n-hexa Noyl 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, and n-pentadecanoyl groups and n-hexadecanoyl groups. 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, and 2,2-dimethylpro Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group and n-hexadecanoyloxy group.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c7 is an alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert -Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group , sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group and isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Moreover, when R ^c7 is a naphthyl alkyl group, the number of carbon atoms of the naphthyl alkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. As a specific example when R ^c7 is a phenylalkyl group, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group are mentioned. Specific examples when R ^c7 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, 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, O, or a heterocyclyl group condensed between these monocyclic groups or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed to be up to 3 in number. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Phthalazine, synnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, 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 1 or 2 organic groups, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkyl groups having 2 to 21 carbon atoms, and 21 or less carbon atoms. Saturated aliphatic acyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms or less which may have a substituent, naphthyl group which may have a substituent, naph which may have a substituent And a naphthyl alkyl group having 11 to 20 carbon atoms and a heterocyclyl group which may have a soil group, a substituent, and the like. Specific examples of these suitable organic ^groups are the same as R ^c7 . As a specific example of the amino group substituted by the organic group of 1 or 2, methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group, etc. Can be lifted.

As a substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^c7 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a number of carbon atoms A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, And dialkylamino groups having an alkyl group of 1 to 6 carbon atoms, morpholine-1-yl group, piperazin-1-yl group, halogen, nitro group and cyano group. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^c7 further has a substituent, the number of the substituents is not limited within a range not impairing the object of the present invention, but 1 to 4 is preferred. When a phenyl group, a naphthyl group, and a 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, R ^c7 is preferably a nitro group or a group represented by R ^c12 -CO-, which tends to improve sensitivity and is preferable. R ^c12 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of the group suitable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Among these groups as R ^c12 , 2-methylphenyl group, thiophen-2-yl group and α-naphthyl group are particularly preferable.

Moreover, when R ^c7 is a hydrogen atom, transparency tends to be good and is preferable. Moreover, if R ^c7 is a hydrogen atom, and R ^c10 is a group represented by the following formula (c4a) or (c4b), transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 are each 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, chain alkyl groups which may have a substituent as R ^c8 and R ^c9 are 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 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. Specific examples when R ^c8 and R ^c9 are a chain alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and 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, And isononyl groups, n-decyl groups, and isodecyl groups. Moreover, when R ^c8 and R ^c9 are an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R ^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 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain alkyl group which has a substituent is linear.

The substituent which an alkyl group may have is not specifically limited in the range which does not inhibit the objective of this invention. Suitable examples of the substituent include cyano group, halogen atom, cyclic organic group and alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom and bromine atom are preferable. Cycloalkyl group, aromatic hydrocarbon group, heterocyclyl group is mentioned as a cyclic organic group. As a specific example of a cycloalkyl group, it is the same as a suitable example when R ^c7 is a cycloalkyl group. As a specific example of an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group, etc. are mentioned. As a specific example of a heterocyclyl group, it is the same as a suitable example when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group included in the alkoxycarbonyl group may be linear or branched, and linear is preferable. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

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

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

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 condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Do. Preferable specific examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, biphenylyl group, anthryl group and phenanthryl group.

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

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or heterocycles condensed between these monocyclic rings or benzene ring. It's Lil. When the heterocyclyl group is a condensed ring, it is assumed to be up to 3 in number. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Phthalazine, synnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran.

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

When the group formed by bonding of 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 a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine ring , Pyrazine ring and pyrimidine ring.

Examples of suitable groups among R ^c8 and R ^c9 described above include groups represented by formulas -A ¹ -A ² . In the formula, A ¹ is a straight chain alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in the straight chain alkylene group of A ¹ is preferably 1 to 10, and more preferably 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and linear is preferable. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, and preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^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 substituents.

Suitable examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phen Alkoxyalkyl groups such as a til group, 6-ethoxy-n-hexyl 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 group cyanoalkyl groups such as -n-heptyl group and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group and Phenyl alkyl groups such as 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-phen Cycloalkyl alkyl groups such as a til 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- Alkoxycarbonylalkyl groups such as ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5 And halogenated alkyl groups such as -heptafluoro-n-pentyl group.

Among R ^c8 and R ^c9 , suitable groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, and 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 -It is a pentyl group.

Examples of suitable organic groups for R ^c10 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, phenyl groups which may have substituents, and substituents similar to R ^c7 . A phenoxy group which may have, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent A naphthoxy group which may have, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a hetero which may have a substituent A cyclyl group, a heterocyclylcarbonyl group optionally having a substituent, an amino group substituted with an organic group of 1 or 2, a morpholine-1-yl group, and Blow binary there may be mentioned 1-yl group and the like. The specific examples of these groups are the same as those described for R ^c7 . Moreover, as ^Rc10 , a cycloalkyl alkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The 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 organic groups, R ^c10 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and a methyl group is most preferred. . Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group included in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and 2 is particularly preferable. Among the cycloalkyl alkyl groups, a cyclopentyl ethyl group is preferable. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and 2 is particularly preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

Moreover, the group represented by -A ³ -CO-OA ⁴ is also preferable as R ^c10 . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

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

Suitable examples of A ⁴ include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Suitable examples of A ⁴ are 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, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group and β-naphthylmethyl group.

Suitable examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyl Oxycarbonylethyl 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-pentyloxy And carbonyl-n-propyl groups, 3-n-hexyloxycarbonyl-n-propyl groups, 3-benzyloxycarbonyl-n-propyl groups, and 3-phenoxycarbonyl-n-propyl groups. have.

Above it has been described for the R ^c10, R ^c10 is preferably a group represented by the following formula (c4a) or (c4b) roneun.

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

^Examples of the organic ^groups for R ^c13 and R ^c14 in the formula (c4a) are the same as R ^c7 . As R ^c13 , an alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 or less and 10 or more, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and 1 is most preferred. 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. As a group represented by formula (c4a), suitable examples of the group in which R ^c13 and R ^c14 form a ring include a naphthalene-1-yl group, 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. Can be mentioned. In the formula (c4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 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 organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

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

In formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms, which may have a substituent, or an aryl group which may have a substituent. As a substituent which R ^c11 may have when it is an alkyl group, a phenyl group, a naphthyl group, etc. are illustrated preferably. Moreover, as a substituent which may be taken 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, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, or a naphthyl group, among them, The methyl group or phenyl group is more preferable.

The compound represented by Formula (c4) is a step of converting the oxime group (> C = N-OH) contained in the compound represented by Formula (c5) described above to an oxime ester group represented by> C = NO-COR ^c11 . It is prepared by a method comprising a. R ^c11 and R ^c11 are the same as in the formula (c4).

The conversion of the oxime group (> C = N-OH) to the oxime ester group represented by> C = NO-COR ^c11 is performed by reacting the compound represented by the formula (c5) with an acylating agent.

Examples of the acylating agent that provides the acyl group represented by -COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O and an acid halide represented by R ^c11 COHal (Hal is a halogen atom).

The following PI-43-PI-83 are mentioned as a suitable specific example of the compound represented by Formula (c4).

Among these, the use of an oxime-based photopolymerization initiator is preferable from the viewpoint of sensitivity, and is an oxime-based compound represented by formula (c1), an oxime ester compound represented by formula (c4), or a fluorene skeleton or carbazolyl skeleton Further, it is more preferable that it is at least one member selected from the group consisting of oxime ester compounds having a nitro group.

In the photosensitive resin composition, the content of the photopolymerization initiator (C) is not particularly limited within a range that does not impair the object of the present invention, the content of the photopolymerization initiator (C) is 0.1% by weight or more with respect to the weight of the solid content of the photosensitive resin composition 20 weight% or less is preferable, and 0.3 weight% or more and 10 weight% or less is more preferable.

<(D) sensitizer>

The photosensitive resin composition may contain the sensitizer (D) together with the photopolymerization initiator (C) above. When the photosensitive resin composition contains (C) a photopolymerization initiator and (D) a sensitizer, it is cured satisfactorily even when a light source having a low irradiation energy such as LED exposure is used.

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

(D) As the sensitizer, a compound having at least one member selected from the group consisting of an alkoxy group, a substituted carbonyloxy group and an oxo group (= O) is preferable as the substituent. As the compound having the substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferable.

The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group and an oxo group (= O), and examples of such a substituent include 1 to 20 carbon atoms. The following alkyl groups, halogenated alkyl groups having 1 to 20 carbon atoms, alkoxy alkyl groups having 2 to 20 carbon atoms, aliphatic acyl groups having 2 to 20 carbon atoms, aromatic acyl groups having 7 to 11 carbon atoms ( Aroyl group), cyano group, nitro group, nitroso group, halogen atom, hydroxyl group and mercapto group.

The alkoxy group may be linear or branched. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 6 or less.

Suitable examples of the alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hex Siloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, n-decyloxy group, etc. are mentioned.

The substituted carbonyloxy group is a group represented by -O-CO-A ^d . A ^d is not particularly limited as long as the sensitizer (D) has a desired sensitizing action, and various organic groups may be used. As A, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms are preferable.

The aryl group or aryloxy group may have 1 or more substituents. The type of the substituent is not particularly limited as long as it does not impair the object of the present invention. When an aryl group or an aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different.

Suitable examples of the substituent include: an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, And aliphatic acyl groups having 2 to 7 carbon atoms, aromatic acyl groups having 7 to 11 carbon atoms (aroyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, and mercapto groups. have.

When A ^d is an alkyl group or an alkoxy group, these groups may be linear or branched.

Suitable examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- And octyl groups and 2-ethylhexyl groups.

Suitable examples of the aryl group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, and the like.

Suitable examples of the alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hex Siloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc. are mentioned.

A condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound substituted by one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group and an oxo group (= O), constituting a condensed ring The number of exchanges to be performed is not particularly limited as long as the desired sensitization action is obtained. 2 or more are preferable, 3 or more are more preferable, 3 or more and 6 or less are especially preferable, and 3 or 4 is the most preferable.

Moreover, as long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the monocyclic ring forming the condensed polycyclic ring may not necessarily be an aromatic ring.

Suitable examples of the condensed polycyclic included in the condensed polycyclic aromatic hydrocarbon compound or condensed polycyclic aromatic heterocyclic compound include acenaphthylene ring, phenanthrene ring, anthracene ring, naphthacene ring, xanthene ring and thioxanthene ring. Among these rings, anthracene ring, naphthacene ring and thioxanthene ring are preferable.

As a compound containing an anthracene ring (D) As a specific example of a compound suitably used as a sensitizer, 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, 9,10 -Bis (n-propylcarbonyloxy) anthracene, 9,10-bis (isopropylcarbonyloxy) anthracene, 9,10-bis (n-butylcarbonyloxy) anthracene, 9,10-bis (isobutylcar Bonyloxy) anthracene, 9,10-bis (n-pentylcarbonyloxy) anthracene, 9,10-bis (n-hexylcarbonyloxy) anthracene, 9,10-bis (n-heptylcarbonyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-octylcarbonyloxy) anthracene, 9,10-bis (n-nonylcarbonyloxy) anthracene, 9,10-bis (n-decylcarbonyloxy) anthracene, 9,10-bis (benzoyloxy) anthracene, 9,10-bis (4-methylbenzoyloxy) anthracene, 9,10-bis (2-naphthoyloxy) anthracene, 2 -Methyl-9,10-bis (acetyloxy) anthracene, 2-methyl-9,10-bis (propionyloxy) anthracene, 2-methyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-methyl-9,10-bis (isopropylcarbonyloxy ) Anthracene, 2-methyl-9,10-bis (n-butylcarbonyloxy) anthracene, 2-methyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-methyl-9,10-bis ( n-pentylcarbonyloxy) anthracene, 2-methyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-methyl-9,10-bis (benzoyloxy) anthracene, 2-methyl-9,10 -Bis (4-methylbenzoyloxy) anthracene, 2-methyl-9,10-bis (2-naphthoyloxy) anthracene, 1-methyl-9,10-bis (acetyloxy) anthracene, 1-methyl-9, 10-bis (propionyloxy) anthracene, 1-methyl-9,10-bis (n-propylcarbonyloxy) anthracene, 1-methyl-9,10-bis (isopropylcarbonyloxy) anthracene, 1-methyl -9,10-bis (n-butylcarbonyloxy) anthracene, 1-methyl-9,10-bis (isobutylcarbonyloxy) anthracene, 1-methyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-methyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-methyl-9,10-bis (benzoyloxy) anthracene, 1-methyl-9, 10-bis (4-methylbenzoyloxy) anthracene, 1-methyl-9,10-bis (2-naphthoyloxy) anthracene, 2-ethyl-9,10-bis (acetyloxy) anthracene, 2-ethyl-9 , 10-bis (propionyloxy) anthracene, 2-ethyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2- Ethyl-9,10-bis (n-butylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-pentylcarbonyl Oxy) anthracene, 2-ethyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (benzoyloxy) anthracene, 2-ethyl-9,10-bis (4- Ethyl-benzoyloxy) anthracene, 2-ethyl-9,10-bis (2-naphthoyloxy) anthracene, 1-ethyl-9,10-bis (acetyloxy) anthracene, 1-ethyl-9,10-bis ( Propionyloxy) anthracene, 1-ethyl-9,10-bis (n-propylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (isopropylcarbonyloxy) anthracene, 1-ethyl-9,10 -Bis (n-butylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 1 -Ethyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (benzoyloxy) anthracene, 1-ethyl-9,10-bis (4-ethyl-benzoyloxy) Anthracene, 1-ethyl-9,10-bis (2-naphthoyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-propylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (isopropylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-butylcarbonyloxy) anthracene, 1- (t-butyl) -9,10- Bis (isobutylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-pentylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-hexyl Carbonyloxy) anthracene, 1 -(t-butyl) -9,10-bis (benzoyloxy) anthracene, 1- (t-butyl) -9,10-bis (4- (t-butyl) -benzoyloxy) anthracene, 1- (t- Butyl) -9,10-bis (2-naphthoyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-propylcarbonyloxy) anthracene, 2- (t-butyl) -9, 10-bis (isopropylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-butylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (iso Butylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-pentylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-hexylcarbonyloxy Anthracene, 2- (t-butyl) -9,10-bis (benzoyloxy) anthracene, 2- (t-butyl) -9,10-bis (4- (t-butyl) -benzoyloxy) anthracene, 2 -(t-butyl) -9,10-bis (2-naphthoyloxy) anthracene, 2-pentyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-pentyl-9,10-bis ( Isopropylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-butylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (iso Tilcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-pentyl-9 , 10-bis (benzoyloxy) anthracene, 2-pentyl-9,10-bis (4- (t-butyl) -benzoyloxy) anthracene and 2-pentyl-9,10-bis (2-naphthoyloxy) anthracene And the like.

Or an anthracene compound substituted with a halogen atom is also preferable as the (D) sensitizer. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.

As anthracene compound substituted with halogen atom, (D) As a specific example of a compound preferable as a sensitizer, 2-chloro-9,10-bis (acetyloxy) anthracene, 2-chloro-9,10-bis (propionyloxy Anthracene, 2-chloro-9,10-bis (n-propylcarbonyloxy) anthracene, 2-chloro-9,10-bis (isopropylcarbonyloxy) anthracene, 2-chloro-9,10-bis ( n-butylcarbonyloxy) anthracene, 2-chloro-9,10-bis (isobutylcarbonyloxy) anthracene, 2-chloro-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-chloro- 9,10-bis (n-hexylcarbonyloxy) anthracene, 2-chloro-9,10-bis (benzoyloxy) anthracene, 2-chloro-9,10-bis (4-methylbenzoyloxy) anthracene, 2- Chloro-9,10-bis (2-naphthoyloxy) anthracene, 1-chloro-9,10-bis (acetyloxy) anthracene, 1-chloro-9,10-bis (propionyloxy) anthracene, 1-chloro -9,10-bis (n-propylcarbonyloxy) anthracene, 1- Chloro-9,10-bis (isopropylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-butylcarbonyloxy) anthracene, 1-chloro-9,10-bis (isobutylcarbonyloxy ) Anthracene, 1-chloro-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-chloro-9,10-bis (Benzoyloxy) anthracene, 1-chloro-9,10-bis (4-methylbenzoyloxy) anthracene, 1-chloro-9,10-bis (2-naphthoyloxy) anthracene, 2-fluoro-9,10 -Bis (acetyloxy) anthracene, 2-fluoro-9,10-bis (propionyloxy) anthracene, 2-fluoro-9,10-bis (n-propylcarbonyloxy) anthracene, 2-fluoro- 9,10-bis (isopropylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (n-butylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (isobutylcarbonyloxy ) Anthracene, 2-fluoro-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-fluoro-9, 10-bis (n-hexylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (benzoyloxy) anthracene, 2-fluoro-9,10-bis (4-methylbenzoyloxy) anthracene, 2- Fluoro-9,10-bis (2-naphthoyloxy) anthracene, 1-fluoro-9,10-bis (acetyloxy) anthracene, 1-fluoro-9,10-bis (propionyloxy) anthracene, 1-fluoro-9,10-bis (n-propylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (isopropylcarbonyloxy) anthracene, 1-fluoro-9,10-bis ( n-butylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (isobutylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (n-pentylcarbonyloxy) anthracene, 1- Fluoro-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (benzoyloxy) anthracene, 1-fluoro-9,10-bis (4-methylbenzoyloxy ) Anthracene, 1-fluoro-9,10-bis (2-naphthoyloxy) anthracene, 2-bromo-9,10-bis (acetyloxy) ) Anthracene, 2-bromo-9,10-bis (propionyloxy) anthracene, 2-bromo-9,10-bis (n-propylcarbonyloxy) anthracene, 2-bromo-9,10-bis (Isopropylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n-butylcarbonyloxy) anthracene, 2-bromo-9,10-bis (isobutylcarbonyloxy) anthracene, 2- Bromo-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-bromo-9,10-bis (benzoyl Oxy) anthracene, 2-bromo-9,10-bis (4-methylbenzoyloxy) anthracene, 2-bromo-9,10-bis (2-naphthoyloxy) anthracene, 1-bromo-9,10 -Bis (acetyloxy) anthracene, 1-bromo-9,10-bis (propionyloxy) anthracene, 1-bromo-9,10-bis (n-propylcarbonyloxy) anthracene, 1-bromo- 9,10-bis (isopropylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-butylcarbonyloxy) anthracene, 1-bromo-9,10-bis (this Sobutylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-hexylcarbonyloxy) anthracene, 1- Bromo-9,10-bis (benzoyloxy) anthracene, 1-bromo-9,10-bis (4-methylbenzoyloxy) anthracene and 1-bromo-9,10-bis (2-naphthoyloxy) And anthracene.

Moreover, the anthracene compound substituted with the alkoxy group is also preferable as a (D) sensitizer.

As an anthracene compound substituted with an alkoxy group, (D) As a specific example of a compound preferable as a sensitizer, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis (n-propyloxy) anthracene , 9,10-bis (n-butyloxy) anthracene, 9,10-bis (n-pentyloxy) anthracene, 9,10-bis (isopentyloxyoxy) anthracene, 9,10-bis (n-hexyloxy City) anthracene, 9,10-bis (n-heptyloxy) anthracene, 9,10-bis (n-octyloxy) anthracene, 9,10-bis (2-ethylhexyloxy) anthracene, 9-methoxyanthracene , 9-ethoxyanthracene, 9- (n-propyloxy) anthracene, 9- (n-butyloxy) anthracene, 9- (n-pentyloxy) anthracene, 9- (isopentyloxyoxy) anthracene, 9- ( n-hexyloxy) anthracene, 9- (n-heptyloxy) anthracene, 9- (n-octyloxy) anthracene, 9- (2-ethylhexyloxy) anthracene, 2-methyl-9,10-dimethoxy Anthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-bis (n-propyloxy) anthracene, 2-methyl-9,10- Bis (n-butyloxy) anthracene, 2-methyl-9,10-bis (n-pentyloxy) anthracene, 2-methyl-9,10-bis (isopentyloxyoxy) anthracene, 2-methyl-9,10 -Bis (n-hexyloxy) anthracene, 2-methyl-9,10-bis (n-heptyloxy) anthracene, 2-methyl-9,10-bis (n-octyloxy) anthracene, 2-methyl-9 , 10-bis (2-ethylhexyloxy) anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-bis (n- Propyloxy) anthracene, 2-ethyl-9,10-bis (n-butyloxy) anthracene, 2-ethyl-9,10-bis (n-pentyloxy) anthracene, 2-ethyl-9,10-bis (iso Pentyloxyoxy) anthracene, 2-ethyl-9,10-bis (n-hexyloxy) anthracene, 2-ethyl-9,10-bis (n-heptyloxy) anthracene, 2-ethyl-9,10-bis (n-octyloxy) anthracene, 2-ethyl-9,10-bis (2-ethylhexyloxy) anthracene, 2-methyl-9-methoxyanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl -9- (n-propyloxy) anthracene, 2-methyl-9- (n-butyloxy) anthra , 2-methyl-9- (n-pentyloxy) anthracene, 2-methyl-9- (isopentyloxyoxy) anthracene, 2-methyl-9- (n-hexyloxy) anthracene, 2-methyl-9- (n-heptyloxy) anthracene, 2-methyl-9- (n-octyloxy) anthracene, 2-methyl-9- (2-ethylhexyloxy) anthracene, 2-ethyl-9-methoxyanthracene, 2- Ethyl-9-ethoxyanthracene, 2-ethyl-9- (n-propyloxy) anthracene, 2-ethyl-9- (n-butyloxy) anthracene, 2-ethyl-9- (n-pentyloxy) anthracene, 2-ethyl-9- (isopentyloxyoxy) anthracene, 2-ethyl-9- (n-hexyloxy) anthracene, 2-ethyl-9- (n-heptyloxy) anthracene, 2-ethyl-9- ( n-octyloxy) anthracene, 2-ethyl-9- (2-ethylhexyloxy) anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro -9,10-bis (n-propyloxy) anthracene, 2-chloro-9,10-bis (n-butyloxy) anthracene, 2-chloro-9,10-bis (n-pentyloxy) anthracene, 2- Chloro-9,10-bis (isopentyloxyoxy) anthracene, 2-chloro Ro-9,10-bis (n-hexyloxy) anthracene, 2-chloro-9,10-bis (n-heptyloxy) anthracene, 2-chloro-9,10-bis (n-octyloxy) anthracene, 2-chloro-9,10-bis (2-ethylhexyloxy) anthracene, 2-bromo-9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo- 9,10-bis (n-propyloxy) anthracene, 2-bromo-9,10-bis (n-butyloxy) anthracene, 2-bromo-9,10-bis (n-pentyloxy) anthracene, 2 -Bromo-9,10-bis (isopentyloxyoxy) anthracene, 2-bromo-9,10-bis (n-hexyloxy) anthracene, 2-bromo-9,10-bis (n-heptyl Oxy) anthracene, 2-bromo-9,10-bis (n-octyloxy) anthracene, 2-bromo-9,10-bis (2-ethylhexyloxy) anthracene, 2-chloro-9-methoxy Anthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9- (n-propyloxy) anthracene, 2-chloro-9- (n-butyloxy) anthracene, 2-chloro-9- (n-pentyl Oxy) anthracene, 2-chloro-9- (isopentyloxyoxy) anthracene , 2-chloro-9- (n-hexyloxy) anthracene, 2-chloro-9- (n-heptyloxy) anthracene, 2-chloro-9- (n-octyloxy) anthracene, 2-chloro-9- (2-ethylhexyloxy) anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9- (n-propyloxy) anthracene, 2-bro Mo-9- (n-butyloxy) anthracene, 2-bromo-9- (n-pentyloxy) anthracene, 2-ethyl-9- (isopentyloxyoxy) anthracene, 2-bromo-9- (n -Hexyloxy) anthracene, 2-bromo-9- (n-heptyloxy) anthracene, 2-bromo-9- (n-octyloxy) anthracene and 2-bromo-9- (2-ethylhexyloxy City) Anthracene etc. are mentioned.

Among the anthracene compounds described above, 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, and 9,10-bis from the viewpoint of ease of manufacture and performance as a sensitizer (D) (n-propylcarbonyloxy) anthracene, 9,10-bis (isopropylcarbonyloxy) anthracene, 9,10-bis (n-butylcarbonyloxy) anthracene, 9,10-bis (isobutylcarbonyloxy ) Anthracene, 9,10-bis (n-hexanoyloxy) anthracene, 9,10-bis (n-heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene and 9,10-dibutoxyanthracene desirable.

As a compound containing a naphthacene ring (D) As a specific example of a compound suitably used as a sensitizer,

2-methyl-5,11-dioxo-6,12-bis (acetyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (propionyloxy) naphthacene, 2-methyl -5,11-dioxo-6,12-bis (n-propylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isopropylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-butylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutylcarbonyloxy) Naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-pentylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-hexyl Carbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-heptylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (Acetyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (propionyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n- Propylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isopropylcarbonyloxy) naphthacene, 2-e -5,11-dioxo-6,12-bis (n-butylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-pentylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-hexylcarbonyloxy Alkyl naphthacene compounds substituted with alkylcarbonyloxy groups such as naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (n-heptylcarbonyloxy) naphthacene;

2-methyl-5,11-dioxo-6,12-bis (benzoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (o-toluoyloxy) naphthacene, 2 -Methyl-5,11-dioxo-6,12-bis (m-toluoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (p-toluoyloxy) naphthacene , 2-methyl-5,11-dioxo-6,12-bis (α-naphthoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (β-naphthoyloxy) Naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (benzoyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (o-toluoyloxy) naphtha Sen, 2-ethyl-5,11-dioxo-6,12-bis (m-toluoyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (p-toluoyloxy) ) Naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (α-naphthoyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (β-naph Aroyloxy group-substituted naphthacene compounds such as toyloxy) naphthacene;

2-methyl-5,11-dioxo-6,12-bis (methoxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (ethoxycarbonyloxy) naphtha Sen, 2-methyl-5,11-dioxo-6,12-bis (n-propyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isopropyloxy Carbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-butyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12- Bis (isobutyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-pentyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo -6,12-bis (n-hexyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-heptyloxycarbonyloxy) naphthacene, 2-methyl -5,11-dioxo-6,12-bis (n-octyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (methoxycarbonyloxy) naphthacene , 2-ethyl-5,11-dioxo-6,12-bis (ethoxycarbonyloxy) naphthacene, 2-ethyl-5 , 11-dioxo-6,12-bis (n-propyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-butyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isobutyloxycarbonyl Oxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-pentyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis ( n-hexyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-heptyloxycarbonyloxy) naphthacene and 2-ethyl-5,11-dioxo Alkoxycarbonyloxy group-substituted naphthacene compounds such as -6,12-bis (n-octyloxycarbonyloxy) naphthacene; And

2-methyl-5,11-dioxo-6,12-bis (phenoxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (o-tolyloxycarbonyl Oxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (m-tolyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (p-tolyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (α-naphthyloxycarbonyloxy) naphthacene, 2-methyl-5,11- Dioxo-6,12-bis (β-naphthyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (phenoxycarbonyloxy) naphthacene, 2-ethyl -5,11-dioxo-6,12-bis (o-tolyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (m-tolyloxycarbonyl Oxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (p-tolyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (α-naphthyloxycarbonyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (β-naphthyloxycarbonyloxy) naphtha And aroyloxycarbonyloxy group-substituted naphthacene compounds such as sen.

Among the compounds containing the above naphthacene ring, 5,11-dioxo-6,12-bis (methoxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (ethoxycarbonyloxy ) Naphthacene, 5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (n-butylcarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (n-pentylcarbonyloxy) naphthacene, 5,11- Dioxo-6,12-bis (n-heptanoyloxy) naphthacene is preferred.

(A) In terms of compatibility with the photopolymerizable compound, 5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (iso Butyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (n-butyryloxy) naphthacene, 5,11-dioxo-6,12-bis (n-valeryloxy) Naphthacene, 5,11-dioxo-6,12-bis (heptanoyloxy) naphthacene is preferred.

(D) As a specific example of the compound containing a thioxanthene ring suitably used as a sensitizer, thioxanthene-9-one, 2-methyl-9H-thioxanthene-9-one, 2-isopropyl- And 9H-thioxanthene-9-one, 1,4-dimethylthioxanthene-9-one, and 3-methyl-9-oxo-9H-thioxanthen-2-yl acetate.

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

<(E) colorant>

The photosensitive resin composition may be a substantially colorless and transparent composition without a colorant depending on its use. On the other hand, in other uses, the photosensitive resin composition may further contain (D) a colorant. The photosensitive resin composition is preferably used as a colorant that is the component (D), for example, by including a black pigment, for example, for forming a black matrix (or black bank) in a color filter of a display device. Moreover, a chromatic colorant can be preferably used, for example, in the use of a display device for forming a color filter.

Although it does not specifically limit as a coloring agent (D) contained in a photosensitive resin composition, When using a coloring agent as a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. Examples of the black pigment include organic oxides, inorganic substances such as metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. Various pigments can be mentioned. Among these, it is preferable to use carbon black having high light-shielding properties.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Moreover, you may use resin-coated carbon black.

Resin-coated carbon black has a lower conductivity than carbon black without resin coating, and thus, when used as a black matrix for liquid crystal display elements such as liquid crystal display displays, displays with low current leakage and high reliability and low power consumption. Can be produced.

Examples of black pigments other than carbon black include (D2a) perylene-based pigments and (D2b) lactam-based pigments. These pigments can be used in combination of two or more.

(D2a) The perylene-based pigment is not particularly limited as long as it is made of a compound having a perylene skeleton and exhibits black color.

(D2a) As a specific example of the perylene-based pigment, the perylene-based pigment represented by the following formula (d-1), the perylene-based pigment represented by the following formula (d-2) and the following formula (d-3) And perylene-based pigments. In commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as the (D2a) perylene-based pigment.

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

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

In formula (d-3), R ^d7 and R ^d8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain N, O, S or P heteroatoms. When R ^d7 and R ^d8 are alkyl groups, the alkyl group may be linear or branched.

The compound represented by the formula (d-1), the compound represented by the formula (d-2) and the compound represented by the formula (d-3) are, for example, Japanese Patent Application Laid-open No. 62-1753, Japan It can be synthesized using the method described in Japanese Patent Publication No. 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its anhydride 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 reprecipitating the obtained preparation in sulfuric acid or recrystallizing in water, an organic solvent, or a mixed solvent of these.

In order to form a cured film having low transmittance for light in a wide wavelength range by dispersing the (D2a) perylene-based pigment well in the photosensitive resin composition, the volume average particle diameter of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less. , 10 nm or more and 500 nm or less are more preferable, and 10 nm or more and 200 nm or less are particularly preferable.

In addition, when the volume particle diameter of the perylene-based pigment is within the above range, it is easy to stably form a cured film having a smooth surface having a low arithmetic average roughness Ra.

(D2b) As a lactam pigment, the compound represented by following formula (d-4) is mentioned, for example.

In formula (d-4), X ^d represents a double bond, and each is an E or Z body independently as a geometric isomer, and R ^d9 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, and chlorine. Represents an atom, a fluorine atom, a carboxy group or a sulfo group, R ^d10 each independently represents a hydrogen atom, a methyl group or a phenyl group, and R ^d11 each independently represents a hydrogen atom, a methyl group or a chlorine atom.

The compound represented by formula (d-4) can be used alone or in combination of two or more.

Since R ^d9 is easy to prepare the compound represented by the formula (d-4), it is preferable to bind to the 6th position of the dihydroindron ring, and R ^d11 is preferably bound to the 4th position of the dihydroindron ring. From the same viewpoint, R ^d9 , R ^d10 and R ^d11 are preferably hydrogen atoms.

The compound represented by formula (d-4) has an EE form, a ZZ form, or an EZ form as a geometric isomer, but any one of them may be a single compound, or a mixture of these geometric isomers.

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

In order to satisfactorily disperse the lactam-based pigment in the photosensitive resin composition, the volume average particle diameter of the lactam-based pigment is preferably 10 nm or more and 1000 nm or less.

Moreover, in order to adjust the color tone of black pigments, such as carbon black, you may add suitably the organic pigment shown below as an auxiliary pigment. Moreover, it is also possible to use a black pigment, such as carbon black, to combine a plurality of organic pigments as shown below, for example, to mix the color materials of the three primary colors to make it black.

As the organic pigment, for example, in the color index (CI; issued by The Society of Dyers and Colourists), a compound classified as a pigment, specifically, the following color index (CI) number It is preferable to use a pigment to which is attached.

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

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

Examples of suitable purple pigments are C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet is the same and only the number is described."), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40 and 50.

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

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

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

In order to uniformly disperse the coloring agent in the photosensitive resin composition, a dispersing agent may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when using carbon black as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

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

The amount of the colorant used in the photosensitive resin composition may be appropriately determined depending on the use of the photosensitive resin composition, but as an example, 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total weight of the components other than the solvent in the photosensitive resin composition Preferably, 5 parts by weight or more and 30 parts by weight or less are more preferable. By setting it as the said range, it is preferable because a black matrix and each colored layer can be formed in a target pattern.

In particular, when forming a black matrix (or black bank) using a photosensitive resin composition, it is preferable to adjust the amount of the light blocking agent in the photosensitive resin composition so that the OD value per 1 µm of the black matrix film is 0.1 or more. When the OD value per 1 µm of the film in the black matrix is 0.1 or more, sufficient display contrast can be obtained when used in the black matrix of the display body.

It is preferable to add a coloring agent to a photosensitive resin composition, after making it into the dispersion liquid disperse | distributed to an appropriate concentration using a dispersing agent.

<Solvent (S)>

The photosensitive resin composition may or may not contain a solvent (S). When the solvent (S) is included, as the solvent (S), for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Poly) alkylene glycol monoalkyl ethers; (Poly) alkylene such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, ethyl pyruvate other esters such as n-propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

The photosensitive resin composition may be prepared by dispersing and dissolving each component in a solvent. If the component (A) described above is liquid, it is not necessary to use a solvent. When a solvent is included, as the solvent used in the photosensitive resin composition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, di Ethylene 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 mono Methyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether , Dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene Recall monoethyl ether and (poly) alkylene glycol monoalkyl ether; (Poly) alkylene such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, ethyl pyruvate other esters such as n-propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

The solvent (S) may be appropriately determined depending on the use of the photosensitive resin composition, but as an example, the solid content concentration in the photosensitive resin composition may be appropriately adjusted within a range of 1% by weight to 50% by weight.

<(E) water repellent>

The photosensitive resin composition may further contain a water repellent agent. Forming a water-repellent film having a pattern shape with a photosensitive resin composition is desirable because, in fields such as flat plate printing plates and inkjet head nozzle surfaces, water-repellent or liquid-repellent properties greatly improve the printing quality. Will be.

(E) The water-repellent agent is not particularly limited, but preferably contains a compound having fluorine. For example, examples of the water repellent include a perfluoroalkyl composition having cationic polymerization and a perfluoropolyether composition having cationic polymerization. Specifically, it is preferably a composition containing a foot ink agent having a side chain comprising a group represented by the following formula (E-1) or a group represented by the following formula (E-2).

-CFXR ^f (E-1)

-(SiR ^e1 R ^e2 -O) _n -SiR ^e3 R ^e4 R ^e5 (E-2)

In formula (1), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f is fluoro of 20 or less carbon atoms in which at least one of the hydrogen atoms which may have an etheric oxygen atom is substituted with a fluorine atom. Alkyl group or fluorine atom.

In formula (2), R ^e1 , R ^e2 , R ^e3 and R ^e4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R ^e5 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, n Represents an integer from 1 to 200.

Moreover, the condensation product containing the hydrolysable silane compound which has a fluorine-containing group and the hydrolysable silane compound which has a cationically polymerizable group can be illustrated. As an example, for example, the following formula

CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OCH ₃ ) ₃

(In the formula, n is an integer of 0 or more and 7 or less.)

The compound etc. which are represented by are mentioned. When n exceeds the above range, compatibility in the photosensitive resin composition decreases, and it becomes difficult to impart uniform water repellency to the entire coating film.

In the photosensitive resin composition, the blending ratio of the water repellent is not particularly limited, but is preferably 20 parts by weight or less, and preferably 0.05 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the total weight of components other than the solvent in the photosensitive resin composition. Is more preferred. When an amount of water repellent in the above range is used, it is easy to achieve a good compatibility between the alkali-soluble resin (A) and the water repellent, while achieving good hardness of the cured film, good water repellency of the cured film, and angular characteristics of a good edge of the cured film.

<Other ingredients>

The photosensitive resin composition may contain various other additives other than this as needed. Specifically, dispersing aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like are exemplified.

As a thermal polymerization inhibitor used for a photosensitive resin composition, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. Moreover, as an antifoaming agent, compounds, such as a silicone type and a fluorine type, can be illustrated, respectively, as compounds, such as anionic type, cationic type, and nonionic.

[Preparation method of photosensitive resin composition]

The photosensitive resin composition is prepared by mixing all the above components with a stirrer. Moreover, when the prepared photosensitive resin composition does not contain insoluble components, such as a pigment, you may filter using a filter so that a photosensitive resin composition becomes uniform.

≪How to form a cured film≫

The manufacturing method of a cured film is a process of forming a photosensitive resin layer by applying a photosensitive resin composition on a substrate (hereinafter simply referred to as a "resin layer forming process"), and a step of selectively exposing the resin layer (hereinafter simply). It includes a process of forming a pattern by developing the exposed photosensitive resin layer with a developer (hereinafter simply referred to as a "development process").

The substrate (substrate or support) can be selected according to various uses, for example, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, etc. Paper, SOG (Spin On Glass), polyester films, polycarbonate films, polymer substrates such as polyimide films, TFT array substrates, PDP electrode plates, glass or transparent plastic substrates, conductive substrates such as ITO and metal, insulating substrates, There are no particular restrictions on semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, and the like. In addition, in the case of forming a laminated structure on a substrate, for example, any layer serving as a substructure already formed on the substrate is included in the concept as a substrate to which a photosensitive resin layer is applied. Moreover, the shape of the base material is not particularly limited, and may be a plate shape or a roll shape. The base material may also have irregularities on the surface by various patterns, for example. In addition, as the substrate, a substrate that is light transmissive or non-transmissive can be selected.

First, in the resin layer forming process, for example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotary coating device), a dispenser, inkjet, spray, screen on a substrate on which a cured product is to be formed. The photosensitive resin composition may be applied using a non-contact type coating device such as printing or curtain flow coater, and, if necessary, the solvent may be removed by drying (prebaking) to form a photosensitive resin layer.

The thickness of the photosensitive resin layer is not particularly limited, but is preferably 0.05 μm or more, more preferably 1 μm or more, even more preferably 7 μm or more, and particularly preferably 10 μm or more. Although there is no upper limit in particular, it is 50 micrometers or less, for example, and 20 micrometers or less are preferable. As described above, since the photosensitive resin composition promotes hardening even in a portion where active energy does not directly contact during exposure, for example, in the aspect of forming a photosensitive resin layer of a thick film having a thickness of 1 µm or more and 15 µm or less, for example , Curing can be sufficiently advanced even in the vicinity of the substrate side distal from the exposure side.

In addition, for the sake of convenience, the photosensitive resin layer filled in the concave portion of the mold, the photosensitive resin composition filled in the concave portion of the substrate having droplets, concavo-convex, etc. It is called.

Then, the formed photosensitive resin layer can be cured by exposure. The exposure method is not particularly limited as long as it is a method capable of curing the photosensitive resin composition, and a heat treatment can also be carried out if necessary.

In exposure, the light source is not particularly limited, and examples thereof include high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, carbon arc lamps, and LEDs. ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, g-ray, i-ray, The coating film may be exposed by irradiation with radiation or electromagnetic waves such as h-ray, j-ray, and k-ray. The exposure to the coated film may be selectively performed through a negative type mask. Although the exposure amount varies depending on the composition of the curable composition, for example, 10 mJ / cm 2 or more and 2000 mJ / cm 2 or less is preferable, 100 mJ / cm 2 or more and 1500 mJ / cm 2 or less is more preferable, and 200 mJ / cm 2 or more and 1200 mJ / cm 2 or less is more preferable. Although exposure roughness differs also depending on the composition of a photosensitive resin composition, it is preferable to set it as 1 mW / cm <2> or more and 50 mW / cm <2> or less.

The temperature at the time of heating is not particularly limited, 180 ° C or more and 280 ° C or less is preferable, 200 ° C or more and 260 ° C or less is more preferable, and 220 ° C or more and 250 ° C or less is particularly preferable. The heating time is preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

The step of curing the photosensitive resin layer is performed by position-selective exposure, and the photosensitive resin layer exposed by position-selection can be developed to obtain a patterned cured film.

The above-mentioned curable composition is difficult to dissolve excessively in a developing solution after exposure. For this reason, by using the above-mentioned curable composition, it is possible to form a patterned cured product having a good shape with an exposed portion as a convex portion and an unexposed portion as a concave portion.

In the developing process, a cured product patterned in a desired shape is formed by developing the exposed coating film with a developer. The developing method is not particularly limited, and an immersion method, a spray method, a paddle method, a dynamic dispenser, or the like can be used.

Specific examples of the developing solution containing the organic solvent include alcohol-based solvents such as PE (propylene glycol monomethyl ether) to glycol ether-based solvents, ether-based solvents such as tetrahydrofuran, ester-based solvents such as butyl acetate, acetone, and the like. And ketone-based solvents such as methyl amyl ketone.

Specific examples of the alkali developer include organic developer such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Further, if necessary, post-baking may be performed on the cured product after exposure or the patterned cured product after development to further advance heat curing. The post-baking temperature is preferably 150 ° C or higher and 270 ° C or lower.

≪Light cargo≫

The cured product is formed by curing the aforementioned curable composition. For this reason, the cured product can also have a good fine pattern, and also has good heat resistance and transparency.

When the cured product is a cured film, the thickness of the cured film is not particularly limited, but is preferably 0.05 μm or more and 50 μm or less.

In addition, the patterned cured film is made of the cured product, and thus can have the above fine pattern.

The cured product may be used as a bank for forming the substrate surface in a partitioned form with a plurality of compartments for dot formation.

In addition, the dot represents the smallest area capable of light modulation in the optical element. For organic EL devices, quantum dot displays, TFT arrays, and thin film solar cells, 1 dot = 1 pixel for black and white display, for example 3 dots (R (red), G (green), for color display), B (blue), etc.) = 1 pixel.

Since the cured product is formed of a photosensitive resin composition having excellent patterning properties, when used in an optical element (especially an organic EL element produced by an inkjet method or a quantum dot display, TFT array or thin film solar cell), the opening The ink can be applied uniformly to form a good dot.

When using the said cured product as a bank use, it is preferable that the width of a bank is 100 micrometers or less, for example, and it is especially preferable that it is 20 micrometers or less. The distance between adjacent banks (pattern width) is preferably 300 µm or less, and particularly preferably 100 µm or less. The height of the bank is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 20 μm.

An example in which a dot is formed by an inkjet method in an opening of a bank for obtaining an optical element using the cured product as a bank application will be described below, but is not limited to this.

A method of manufacturing a quantum dot display, which is an example of an optical element, using a bank formed on a substrate (for example, a bank formed in a planar grid shape) will be described.

Here, the bank on the substrate is formed so that the openings match the dot pattern of the quantum dot display to be manufactured.

Further, the substrate is formed by depositing a light-transmitting electrode such as ITO on a light-transmitting substrate such as glass by sputtering or the like. The light-transmitting electrode may be patterned as necessary.

Ink is dropped from the inkjet head into the opening surrounded by the bank to inject a predetermined amount of ink into the opening. As the ink, an ink known for quantum dot display according to the function of the dot (for example, an ink using a material for a hole injection layer, a hole transport layer, a quantum dot layer, a hole blocking layer, and an electron injection layer) It is selected and used.

Then, depending on the type of ink used, for example, for removal or curing of the solvent, drying and / or heating or the like is performed to form a desired dot layer in a form adjacent to the bank. Thereafter, a reflective electrode such as aluminum or a transparent electrode such as ITO is formed by a vapor deposition method or the like to obtain a quantum dot display.

Further, the quantum dot display may be a blue light conversion type quantum dot display. In this case, a bank is formed in a lattice shape in a plan view according to the outline of each dot on a transparent substrate such as glass. Next, in the opening for dot formation, a nanoparticle solution that converts blue light into green light by an inkjet method, a nanoparticle solution that converts blue light into red light, and, if necessary, a blue color ink is applied and dried to produce a module. By using a blue color light source as a backlight and using the module as a color filter replacement, a display having excellent color reproducibility can be obtained.

By using the bank of the cured product according to the present invention, it is possible to uniformly apply ink to an opening partitioned with a cured product (bank) having a high degree of patterning during the manufacturing process, thereby making the optical having a dot formed with good precision. Devices (organic EL devices, quantum dot displays, TFT arrays or thin film solar cells) can be obtained.

[Example]

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

In Examples 1 to 23 and Comparative Examples 1 to 5 shown below, as the alkali-soluble resin (A), the resins (a-1-1) and (a-1-2) were added in amounts shown in Table 1, respectively. And (a-2-1).

First, 235 g of bisphenol fluorene-type epoxy resin (epoxy equivalent 235) and 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid in a 500 ml four-necked flask Was added, and heated and dissolved at 90 ° C to 100 ° C while blowing air at a rate of 25 mL / minute. Subsequently, the solution was gradually heated while being cloudy, and heated to 120 ° C to dissolve completely. Here, the solution gradually became a transparent consistency, but stirring was continued as it was. In the meantime, heating and stirring was continued until the acid value was measured and became less than 1.0 mg KOH / g. It took 12 hours to reach the target. Then, it was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate.

Next, 600 g of 3-methoxybutyl acetate was added and dissolved in 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, followed by dissolution, followed by mixing 80.5 g of biphenyltetracarboxylic acid anhydride and 1 g of tetraethylammonium bromide. Then, the temperature was gradually increased and reacted at 110 ° C to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride, 38.0 g of 1,2,3,6-tetrahydro phthalic anhydride were mixed and reacted at 90 ° C for 6 hours to obtain a resin (a-1-1) (weight average molecular weight: 3400). . The disappearance of the acid anhydride was confirmed by IR spectrum.

In the production of the resin (a-1-1), in the same manner as in the production of the resin (a-1-1), except that 80.5 g of biphenyltetracarboxylic acid anhydride was replaced with 59.7 g of pyromellitic acid anhydride. Resin (a-1-2) was obtained. The weight average molecular weight was 2500.

(In the above formula of acrylic resin a-2-1, the number at the bottom right of each unit means the content (% by weight) of each unit in the alkali-soluble resin.)

The weight average molecular weight of the alkali-soluble resin was 7000.

Moreover, in each Example and the comparative example, dipentaerythritol hexaacrylate (b-2-1) was used as a polyfunctional (meth) acrylic monomer (B2) as a crosslinking agent (B).

In addition, the compounds represented by the following formulas (b-1-1) to (b-1-4) as monofunctional (meth) acrylic monomers as the crosslinking agent (B) were used in the amounts shown in Table 1, respectively.

In each of Examples and Comparative Examples, compounds c1 to c2 represented by the following formula were used as the photopolymerization initiator (C).

Moreover, in each Example and a comparative example, 2-isopropyl thioxanthone (compound d1: 2-isopropyl-9H-thioxanthene-9-one) was used as a sensitizer (D).

In each of Examples 1 to 18, 22 to 26, and Comparative Examples 1 to 4, carbon was used as the colorant (E) in the compounding amount as shown in Table 1 (the compounding amount converted to the number of only the colorant component in each dispersion). Black dispersion (in PGMEA solvent, 27% by weight of thermal black) (e1), or organic pigment mixed black (in PGMEA solvent, 20% by weight of organic pigment (Red-256 / Violet-23 / Blue-156 = 40/20 / 40 (weight ratio))) (e2) was used.

In each of the Examples and Comparative Examples, as the additive (F), from the active agents (f1: BYK310) and (f3) fluorine-based surfactants (perfluorobutyl ethyl methacrylate and polyethylene glycol methacrylate and n-butyl methacrylate) A copolymer containing a derived structural unit, weight average molecular weight: 20000), and N-phenyl-3-aminopropyltrimethoxysilane (f2) were added as an additive.

In the examples, all of these active agents (f1), (f3) and additives (f2) were added. However, in the photosensitive resin composition, these active agents and additives are not essential components, and the same evaluation results as those in the examples disclosed herein are obtained even in the same composition except that these are not blended.

In each example and comparative example, 3-methoxybutyl acetate (g1) and propylene glycol monomethyl ether acetate (g2) were used as a solvent in a ratio of 15/85 (weight ratio).

[Examples 1 to 26 and Comparative Examples 1 to 5]

Alkali-soluble resins (A), crosslinking agents (B), photopolymerization initiators (C), sensitizers (D), colorants (E), additives (E) and solvents (G) in the types and amounts listed in Table 1 below are at room temperature. The mixture was uniformly mixed in a stirrer at (25 ° C ± 2 ° C) to obtain photosensitive resin compositions of Examples and Comparative Examples. Moreover, in Examples 19-21 and Comparative Example 5, the coloring agent (E) was not mix | blended, and it was set as the transparent resin composition.

[Line pattern evaluation]

The photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were coated on a glass substrate (100 mm × 100 mm) using a spin coater, and prebaked at 100 ° C. for 120 seconds to form a coating film. Subsequently, the coating film was irradiated with ultraviolet light through a negative type mask having a line pattern of 20 µm in width with an exposure gap of 50 µm using a Proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Co., Ltd.). The exposure amount was 200 mJ / cm 2. A line pattern having a film thickness of 10 µm was formed as a cured film by developing the coated film after exposure with a 0.04 wt% KOH aqueous solution at 26 ° C for 50 seconds, and then post-baking at 230 ° C for 30 minutes.

(Pattern straightness evaluation)

The formed line pattern was observed with an optical microscope to evaluate the pattern straightness. The straightness of the pattern was evaluated as "good" when there was no shaking at the edge of the line and "bad" when there was shaking.

(Taper angle)

The taper angle was evaluated about the line pattern formed with the exposure amount of 200 mJ / cm <2>. About the taper angle, it measured using the scanning electron microscope as the bonding angle between a pattern and a board | substrate. Table 1 shows the measured taper angle. The taper angle closer to 90 ° means that the shape of the cross section of the pattern is closer to the desired rectangular shape. When the taper angle is an angle significantly smaller than 90 °, the shape of the pattern cross section is not a desired rectangular shape. Moreover, the cross-sectional shape of the line pattern was judged based on the following judgment criteria based on the measurement result of the taper angle. Table 1 shows all the results.

◎: The taper angle is 80 ° or more and 90 ° or less.

○: The taper angle is 70 ° or more but less than 80 °.

(Triangle | delta): The taper angle is 50 degrees or more and less than 70 degrees.

×: The taper angle is less than 50 °.

[Evaluation of OD value]

The photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and prebaked at 100 ° C. for 120 seconds to form a coating film. Next, a photosensitive resin layer was exposed using a proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) with an exposure amount of 200 mJ / cm 2 and an exposure gap of 50 μm. A cured film was formed by post-baking the exposed photosensitive resin layer at 230 ° C for 30 minutes. The formed light-shielding film had a thickness of 10 μm. The OD value per 10 µm of the formed light-shielding film was measured using a transmittance meter (D-200II, manufactured by Gretagmark Beth), and an OD value per 1 µm was calculated using an approximate curve. Table 1 shows the measurement results of the OD values.

It can be seen that the OD values of the cured films formed using the photosensitive resin compositions of Examples 1 to 18, 22 to 26, and Comparative Examples 1 to 4 containing a black colorant were all 0.45 / m, and cured films having excellent light shielding properties were formed. have. On the other hand, it can be seen that the OD values of the cured films formed using the photosensitive resin compositions of Examples 19 to 21 and Comparative Example 5, which do not contain a colorant, were all 0.01 / m, and cured films having high transmittance were formed.

Claims (13)

Alkali-soluble resin (A);
Crosslinking agent (B);
As a photosensitive resin composition comprising a photopolymerization initiator (C);
A photosensitive resin composition comprising a monofunctional (meth) acrylic monomer (B1) having a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent as the crosslinking agent (B). The method according to claim 1,
A photosensitive resin composition in which the monofunctional (meth) acrylic monomer (B1) comprises a monofunctional (meth) acrylic monomer (B1a) having a biphenyl skeleton. The method according to claim 2,
The monofunctional (meth) acrylic monomer (B1a) photosensitive resin composition comprising a compound represented by the following formula (B1-1):
CH ₂ = CR ^b1 -CO- (OR ^b2- ) _n1 -X ^b1 -BP ... (B1-1)
In formula (B1-1), R ^b1 is a hydrogen atom or a methyl group, R ^b2 is an alkylene group having 1 to 4 carbon atoms, BP is a biphenyl group which may have a substituent, and n1 is 0 to 10 When n1 is 0, X ^b1 is -O- or -NH-, and when n1 is an integer of 1 to 10, X ^b1 is -O-, -NH-, -O-CO- *,- NH-CO- *, -O-CO-O- and -NH-CO-O- * is a linking group selected from the group consisting of a linking group with an * for an asymmetric linking group among the linking groups, which bonds with BP Hands. The method according to any one of claims 1 to 3,
A photosensitive resin composition further comprising a polyfunctional (meth) acrylic monomer (B2) as the crosslinking agent (B). The method according to claim 4,
A photosensitive resin composition in which the polyfunctional (meth) acrylic monomer (B2) is bifunctional or higher. The method according to any one of claims 1 to 5,
A photosensitive resin composition comprising a resin having a cardo structure as the alkali-soluble resin (A). The method according to any one of claims 1 to 6,
The photosensitive resin composition wherein the content of the monofunctional (meth) acrylic monomer (B1) is 5% by weight or more and 50% by weight or less with respect to the total weight of the crosslinking agent (B). The method according to any one of claims 1 to 7,
A photosensitive resin composition further comprising a sensitizer (D). The method according to any one of claims 1 to 8,
A photosensitive resin composition further comprising a colorant (E). The method according to claim 9,
The coloring agent (E) is a black pigment photosensitive resin composition. The method according to any one of claims 1 to 10,
A photosensitive resin composition further comprising a water repellent (F). Forming a photosensitive resin layer by applying the photosensitive resin composition according to any one of claims 1 to 11 on a substrate;
Positionally exposing the photosensitive resin layer;
Developing the patterned cured film comprising; developing the exposed photosensitive resin layer with a developer. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 11.