TW201643211A - Photosensitive resin compositon, pattern forming method, cured film, insulating film, color filter, and display device - Google Patents

Abstract

The subject of the present invention is to provide a negative type photosensitive resin composition capable of forming a pattern having excellent adhesion at a low exposure amount, a pattern forming method using the negative type photosensitive resin composition, a cured film formed by using the negative type photosensitive resin composition, an insulating film, a color filter, and a display device having the cured film, insulating film, or color filter. The solution means for the negative type photosensitive resin composition contains compound represented by formula (1). (In formula (1), R1 is a hydrogen atom or an alkyl group, R2 is an aromatic group which may have a substituent, R3 is an alkylene group which may have a substituent, R4 is each independently a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n is an integer of 0~3.).

Description

Photosensitive resin composition, pattern forming method, cured film, insulating film, color filter, and display device

The present invention relates to a photosensitive resin composition, a pattern forming method using the photosensitive resin composition, a cured film formed using the photosensitive resin composition, an insulating film, a color filter, and the cured film. , an insulating film, or a color filter display device.

The negative photosensitive resin composition in the photosensitive resin composition has a property of being cured by irradiation with electromagnetic waves such as ultraviolet rays. The negative photosensitive resin composition can be used for a display device, a semiconductor device, an electronic component, a microelectromechanical system (MEMS), etc., by curing a portion irradiated with electromagnetic waves to obtain a desired shape. use. For example, in a display device, it is used as a material such as a planarization film, an insulating film, a color filter, a black matrix, a spacer, and a partition in a liquid crystal display, an organic EL display, or the like. Further, in the case of a positive photosensitive resin composition, it may be obtained by irradiation with electromagnetic waves such as ultraviolet rays and development. To the step of thermal hardening, etc., a hardened material is obtained.

As such a photosensitive resin composition, in order to secure the reliability of the product, it is required to adhere to the high adhesion of the substrate when forming a minute pattern. Therefore, a photosensitive resin composition containing an amine-based decane coupling agent has been proposed as an adhesion enhancer (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-035670

In other words, in recent years, from the viewpoint of further improving productivity, a photosensitive resin composition capable of forming a pattern having a good shape with a low exposure amount is required.

However, when an amine-based decane coupling agent is contained as an adhesion enhancer as in Patent Document 1, the adhesion to the substrate is improved, but the amount of exposure necessary for pattern formation increases.

The present invention has been made in view of the above-mentioned problems, and an object of the invention is to provide a photosensitive resin composition capable of forming a pattern having excellent adhesion with a low exposure amount, a pattern forming method using the photosensitive resin composition, and the like. A cured film formed of a photosensitive resin composition, an insulating film, a color filter, and a display device including the cured film, the insulating film, or a color filter.

The inventors of the present invention have repeated efforts to achieve the above object. As a result, it has been found that the above problems can be solved by including a specific compound in the photosensitive resin composition, and the present invention has been completed. In particular, the present invention provides the following.

The first aspect of the present invention is a photosensitive resin composition containing a compound represented by the following formula (1).

(In the formula (1), R ¹ is a hydrogen atom or an alkyl group, R ² is an aromatic group which may have a substituent, R ³ is an alkylene group which may have a substituent, and R ⁴ each independently represents a halogen atom; Hydroxy, mercapto, thioether, decyl, decyl, nitro, nitroso, sulfonato, phosphino, phosphinyl, phosphonato, or organic , n is an integer from 0 to 3.)

The second aspect of the present invention is a pattern forming method in which a coating film or a molded body is formed by using the photosensitive resin composition of the present invention, and the coating film or the molded body is irradiated with a specific pattern of electromagnetic waves.

The third aspect of the present invention is a cured film formed using the photosensitive resin composition of the present invention.

A fourth aspect of the invention is the use of the photosensitivity of the invention An insulating film formed of a resin composition.

The fifth aspect of the present invention is a color filter formed using the photosensitive resin composition of the present invention.

A sixth aspect of the present invention is a display device comprising the cured film, the insulating film, or the color filter of the present invention.

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern having excellent adhesion with a low exposure amount, a pattern forming method using the photosensitive resin composition, and a hardening formed using the photosensitive resin composition. A film, an insulating film, a color filter, and a display device including the cured film, the insulating film, or a color filter.

"Photosensitive Resin Composition"

In the present specification, the "photosensitive resin composition" generally includes a negative photosensitive resin composition and a positive photosensitive resin composition unless otherwise specified.

<Compound represented by formula (1)>

The photosensitive resin composition of the present invention is a photosensitive resin composition containing a compound represented by the following formula (1). Hereinafter, the compound represented by the formula (1) will be described first, and then the photosensitive resin composition will be described.

(In the formula (1), R ¹ is a hydrogen atom or an alkyl group, R ² is an aromatic group which may have a substituent, R ³ is an alkylene group which may have a substituent, and R ⁴ is a halogen atom, a hydroxyl group, a decyl group, Thioether, decyl, decyl, nitro, nitroso, sulfonate, phosphino, phosphinyl, phosphonate, or organic, n is an integer from 0 to 3).

In the formula (1), R ¹ is a hydrogen atom or an alkyl group. When R ¹ is an alkyl group, the alkyl group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5.

Specific examples of a suitable alkyl group as R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n- group. Pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-fluorenyl, n-fluorenyl, n-undecane Base, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl , n-nonadecyl, and n-eicosyl.

In the formula (1), R ² is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent, or may be an aromatic heterocyclic group which may have a substituent.

The kind of the aromatic hydrocarbon group is not particularly limited insofar as it does not inhibit the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, or may be formed by bonding a single or two aromatic hydrocarbon groups by a single bond. The aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group or a phenanthryl group.

The kind of the aromatic heterocyclic group is not particularly limited insofar as it does not inhibit the object of the present invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzo is preferred. Thiazolyl, and benzimidazolyl.

The phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group may have a substituent, and examples thereof include a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl group, a nitro group, a nitroso group, and a sulfinic group. An acid group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, an amine group, an ammonium group, and an organic group. When the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the aromatic group is an organic group, the organic group may, for example, be an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. The organic group may contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring. The organic group is usually monovalent, but in the case of forming a cyclic structure or the like, it may be an organic group having two or more valences.

When the aromatic group has a substituent on a carbon atom adjacent thereto, The two substituents bonded to the adjacent carbon atoms may also be bonded to form a ring structure. The cyclic structure may be an aliphatic hydrocarbon ring or an aliphatic ring containing a hetero atom.

When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group may contain an oxygen atom, a nitrogen atom, or a ruthenium atom. The bond of a hetero atom. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, a urethane bond, and an imido bond (-N=C ( -R)-, -C(=NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinium bond, an azo bond or the like.

The organic group may have a bond containing a hetero atom, and is preferably an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, or the like, from the viewpoint of heat resistance of the compound represented by the formula (1). An amino group bond (-NR-: R represents a hydrogen atom or a monovalent organic group) urethane bond, an imido bond (-N=C(-R)-, -C(=NR)-:R represents A hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinium bond.

When the organic group is a substituent other than the hydrocarbon group, the kind of the substituent other than the hydrocarbon group is not particularly limited insofar as it does not inhibit the object of the present invention. Specific examples of the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, and a decane group. Base, sterol group, alkoxy group, alkoxycarbonyl group, amine group, monoalkylamino group, dialkyl aluminum group, monoarylamine group, diarylamine group, aminomethylcarbenyl group, thio group Aminomethyl sulfonyl, nitro, nitroso, carboxylate, sulfhydryl, decyloxy, sulfinate, sulfonate A group, a phosphino group, a phosphinyl group, a phosphonate group, an alkyl ether group, an alkenyl ether group, an alkyl sulfide group, an alkenyl sulfide group, an aryl ether group, an aryl sulfide group, and the like. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of a linear chain, a branched chain, and a cyclic group.

The substituent of the phenyl group, the polycyclic aromatic hydrocarbon group or the aromatic heterocyclic group is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. An alkoxy group, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom.

As R ² , a compound represented by the formula (1) can be synthesized inexpensively and easily, and the solubility of the imidazole compound in water or an organic solvent is preferably a phenyl group, a furyl group or a thiophene group which may have a substituent. base.

In the formula (1), R ³ is an alkylene group which may have a substituent. The alkylene group may have a substituent, and is not particularly limited insofar as it does not hinder the object of the present invention. Specific examples of the substituent which the alkylene group may have include a hydroxyl group, an alkoxy group, an amine group, a cyano group, and a halogen atom. The alkylene group may be a linear alkyl group or a branched alkyl group, preferably a linear alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, and is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 5. Further, among the carbon atoms of the alkyl group, the carbon atom bonded to the substituent of the alkyl group is not contained.

The alkoxy group which is bonded to the substituent of the alkylene group may be a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.

The amine group bonded to the substituent of the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or the dialkylamine group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.

Specific examples of the suitable alkylene group as R ³ include a methylene group, an ethane-1,2-diyl group, an n-propane-1,3-diyl group, and an n-propane-2,2-diyl group. , n-butane-1,4-diyl, n-pentane-1,5-diyl, n-hexane-1,6-diyl, n-heptane-1,7-diyl, n -octane-1,8-diyl, n-decane-1,9-diyl, n-decane-1,10-diyl, n-undecane-1,11-diyl, n- Dodecane-1,12-diyl, n-tridecane-1,13-diyl, n-tetradecane-1,14-diyl, n-pentadecane-1,15-diyl, N-hexadecane-1,16-diyl, n-heptadecane-1,17-diyl, n-octadecane-1,18-diyl, n-nonadecane-1,19-di And n-eicosane-1,20-diyl.

R ⁴ is a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is An integer from 0 to 3. When n is an integer of 2 to 3, a plurality of R ^{4 's} may be the same or different.

When R ⁴ is an organic group, the organic group is the same as the organic group which the aromatic group may have as a substituent with respect to R ² .

When R ⁴ is an organic group, an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are preferable as the organic group. The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms; more preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group. The aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group or a phenanthryl group; more preferably a phenyl group or a naphthyl group; and particularly preferably a phenyl group. As the aromatic heterocyclic group, pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzo is preferred. Thiazolyl, and benzimidazolyl; more preferably furyl, and thienyl.

When R ⁴ is an alkyl group, the bonding position of the alkyl group on the imidazole ring is preferably 2, 4 or 5; more preferably 2. When R ⁴ is an aromatic hydrocarbon group or an aromatic heterocyclic group, the bonding position of these groups on the imidazole is preferably 2 positions.

Among the compounds represented by the above formula (1), those which are inexpensive and can be easily synthesized, and which have excellent solubility in water or an organic solvent are preferably compounds represented by the following formula (1-1); more preferably It is a compound represented by the formula (1-1) and R ³ is a methylene group.

(In the formula (1-1), R ¹ , R ³ , R ⁴ and n are the same as those in the formula (1), and R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen. Atom, halogen atom, hydroxyl group, mercapto group, thioether group, nonylalkyl group, decyl group, nitro group, nitroso group, sulfinic acid group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphinium group, a phosphonate group, an amine group, an ammonium group, or an organic group, wherein at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom).

When R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are an organic group, the organic group is the same as the organic group which R ² in the formula (1) has as a substituent. R ⁵ , R ⁶ , R ⁷ and R ^{8 are} preferably a hydrogen atom from the viewpoint of solubility of the imidazole compound in a solvent.

In particular, at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably the following substituent; particularly preferably, R ⁹ is the following substituent. When R ⁹ is a substituent described below, it is preferred that R ⁵ , R ⁶ , R ⁷ and R ⁸ are a hydrogen atom.

-OR ¹⁰ (R ¹⁰ is a hydrogen atom or an organic group).

When R ¹⁰ is an organic group, the organic group is the same as the organic group which R ² in the formula (1) has as a substituent. R ^{10 is} preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, most preferably a methyl group.

Among the compounds represented by the above formula (1-1), a compound represented by the following formula (1-1-1) is preferred.

(In the formula (1-1-1), R ¹ , R ⁴ and n are the same as those in the formula (1), and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom. , hydroxy, mercapto, thioether, decyl, decyl, nitro, nitroso, sulfinate, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphonate An amine group, an ammonium group or an organic group, wherein at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a group other than a hydrogen atom).

Among the compounds represented by the formula (1-1-1), at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is preferably a group represented by the above -OR ¹⁰ ; particularly preferably R ¹⁵ is the base represented by -OR ¹⁰ . When R ¹⁵ is a group represented by -OR ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ^{14 are} preferably a hydrogen atom.

The method for synthesizing the compound represented by the above formula (1) is not particularly limited. For example, the above formula (1) can be synthesized by reacting a halogen-containing carboxylic acid derivative represented by the following formula (I) with an imidazole compound represented by the following formula (II) in accordance with a general method to carry out imidylation. ) the compound indicated.

(In the formulae (I) and (II), R ¹ , R ² , R ³ , R ⁴ and n are the same as those in the formula (1). In the formula (I), Hal is a halogen atom).

In addition, when the imidazole compound is a compound represented by the formula (1) and R ³ is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (1-1), it may be described below. A method resulting from the Michael addition reaction to synthesize an imidazole compound.

(In the formula (1-2), R ¹ , R ² , R ⁴ and n are the same as those in the formula (1)).

Specifically, for example, a 3-substituted acrylic acid derivative represented by the following formula (III) and an imidazole compound represented by the above formula (II) can be mixed in a solvent to cause a Michael addition reaction to obtain the above formula. (1-2) an imidazole compound represented.

(In the formula (III), R ¹ , R ² , R ⁴ and n are the same as those in the formula (1)).

In addition, the imidazole group-containing 3-substituted acrylic acid derivative represented by the following formula (IV) can be added to a water-containing solvent to obtain an imidazole compound represented by the following formula (1-3).

(In the formula (IV) and the formula (1-3), R ² , R ⁴ and n are the same as in the formula (1)).

In this case, the imidazole compound represented by the above formula (II) and the 3-substituted acrylic acid represented by the following formula (V) are produced by hydrolysis of the 3-substituted acrylic acid derivative represented by the above formula (IV). Then, a Michael addition reaction is carried out between the 3-substituted acrylic acid represented by the following formula (V) and the imidazole compound represented by the above formula (II) to form an imidazole compound represented by the above formula (1-3).

(In the formula (V), the R ² system is the same as the formula (1)).

Specific examples of suitable compounds represented by the formula (1) include the following.

The compound represented by the above formula (1) is excellent in solubility in an organic solvent, and when it is contained in a photosensitive resin composition, good micro patterning properties can be obtained.

Further, the compound can be synthesized as in the examples described below.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention can be used by adding a compound represented by the above formula (1) to a conventionally known photosensitive resin composition without any particular limitation. Hereinafter, specific examples of the photosensitive resin composition of the present invention will be described in detail.

In addition, the photosensitive resin composition preferably has a compound represented by the above formula (1), an alkali-soluble resin, a photopolymerization initiator, a photosensitizer, and an organic solvent, but is not limited to the following specific examples. A photopolymerizable monomer can also be used as needed.

The alkali-soluble resin may, for example, be a conventionally known resin having an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group or a sulfo group (-SO ₃ H). The skeleton of the resin having an alkali-soluble group is not particularly limited, and examples thereof include a resin having a cardo structure, a polyimide resin, an epoxy resin, a (meth)acrylic resin, and a (hydroxy)styrene system. A resin, or a ruthenium resin such as polydecane or polydecane. The alkali-soluble resin preferably contains a resin selected from the group consisting of a resin having a cardo structure, a resin having a phenolic hydroxyl group, a polyimide resin, and an epoxy resin. The details of the photopolymerization initiator, the sensitizer, the organic solvent, and the photopolymerizable monomer are also described in the photosensitive resin compositions of the first to seventh aspects described later.

(1) photosensitive resin composition of the first aspect

The photosensitive resin composition of the first aspect is a negative photosensitive resin composition containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the above formula (1), and an organic solvent.

The alkali-soluble resin in the photosensitive resin composition of the first aspect is not particularly limited, and a conventionally known alkali-soluble resin can be used. The alkali-soluble resin may be one having an ethylenically unsaturated group or not having an ethylenically unsaturated group.

Furthermore, in the present specification, an alkali-soluble resin means a resin-concentrated 20% by mass of a resin solution (solvent: propylene glycol monomethyl ether acetate), a resin film having a film thickness of 1 μm was formed on a substrate, and immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute. When the film thickness is 0.01 μm or more, it is dissolved.

The alkali-soluble resin having an ethylenically unsaturated group can be, for example, a resin obtained by further reacting a polybasic acid anhydride with a reactant of an epoxy compound and an unsaturated carboxylic acid.

Among them, a resin represented by the following formula (a-1) is preferable. The resin represented by the formula (a-1) is preferred from the viewpoint of high photocurability.

In the above formula (a-1), X ^a represents a group represented by the following formula (a-2).

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

Further, in the above formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylnemethine tetrahydrogen Phthalic anhydride, chloro-bromic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

Further, in the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

Further, in the above formula (a-1), m represents an integer of 0 to 20.

Further, an alkali-soluble resin having an ethylenically unsaturated group may be a polyester obtained by reacting (meth)acrylic acid with a polyester prepolymer obtained by condensing a polyol with a monobasic acid or a polybasic acid. Acrylate; a urethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups, and reacting a (meth)acrylic acid; and a bisphenol A type epoxy Resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol Aldehyde resin type epoxy resin, trisphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type ring An epoxy resin such as an oxygen resin, or a (meth)acrylic epoxy resin obtained by reacting with (meth)acrylic acid.

In the present specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means both acrylate and methacrylate.

On the other hand, as the alkali-soluble resin having no ethylenically unsaturated group, an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic group-containing unsaturated compound may be used. A resin obtained by copolymerization.

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and these dicarboxylic acids; Acid anhydride and the like. Among these, (meth)acrylic acid and maleic anhydride are particularly preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 3,4-cyclo(meth)acrylate. Oxybutyl butyl ester, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 4-oxatetracyclo(methyl)acrylate-[6.2 .1.0 ^2,7 0 ^3,5 ]undecyl ester (meth)acrylic acid epoxy alkyl esters; α-ethyl glycidyl acrylate, α-n-propyl methacrylate glycidyl ester, α- Α-alkyl acrylate epoxy alkyl esters such as n-butyl acrylate glycidyl ester, α-ethyl acrylate 6,7-epoxy heptyl, etc.; o-vinylbenzyl glycidyl ether, m-ethylene A glycidyl ether such as a benzyl glycidyl ether or a p-vinylbenzyl glycidyl ether. Among these, from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like, in particular, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, or (meth)acrylic acid Preferably, 6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

The unsaturated compound containing an alicyclic group is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be a single ring or a polycyclic ring. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, the alicyclic group-containing unsaturated compound may, for example, be a compound represented by the following formula.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^{a4 is} preferably a single bond, a linear or a branched chain alkyl group such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, methylene , hexamethylene. R ^{a5 is} preferably, for example, a methyl group or an ethyl group.

The proportion of the constituent unit derived from the above unsaturated carboxylic acid in the alkali-soluble resin is preferably from 3 to 25% by mass, more preferably from 5 to 25% by mass. Further, the ratio of the constituent unit derived from the epoxy group-containing unsaturated compound is preferably from 71 to 95% by mass, more preferably from 75 to 90% by mass. Further, the ratio of the constituent unit derived from the alicyclic group-containing unsaturated compound is preferably from 1 to 25% by mass, more preferably from 3 to 20% by mass, still more preferably from 5 to 15% by mass. When it is in the above range, the alkali solubility of the obtained resin can be made moderate, and the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing can be improved.

The mass average molecular weight of the alkali-soluble resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By having the above range, good developability can be obtained, and sufficient heat resistance and film strength can be obtained.

The content of the alkali-soluble resin is preferably from 5 to 80% by mass, and more preferably from 15 to 50% by mass, based on the solid content of the photosensitive resin composition of the first aspect. When it is in the above range, the balance of developability tends to be easily obtained.

The photopolymerizable monomer in the photosensitive resin composition of the first aspect is a monofunctional monomer and a polyfunctional monomer.

Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) propylene oxime. Amine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl ( Methyl) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, anhydrous citraconic acid, crotonic acid, 2-propenylamine 2-methylpropane sulfonic acid, tert-butyl propylene decyl sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-(meth) acrylate Ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (methyl) ) 2-phenoxy-2-hydroxypropyl acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, tetrahydrofuran methyl (methyl) Acrylate, dimethylamino (meth) acrylate, glycidol (meth) acrylate Ester, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth) acrylate of phthalic acid derivatives Wait. These monofunctional monomers may be used alone or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(a). Acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di Methyl) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2, 2- bis ( 4-(methacryloxyloxydiethoxyphenyl)propane, 2,2-bis(4-(methacryloxypolyethoxyphenyl)propane, 2-hydroxyl (meth)acrylate -3-(Methyl) propylene methoxypropyl ester, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether (Meth) acrylate, diglycidyl diglycol di(meth) acrylate, glycerin triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, urethane (methyl) Reaction of acrylate (i.e., toluene diisocyanate), trimethylhexamethylene diisocyanate with hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylene a polyfunctional monomer such as a bis(meth)acrylamide, a (meth) acrylamide methyl ether, a condensate of a polyol and N-methylol (meth) acrylamide, or triacrylate Triacrylformal and the like. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, based on the solid content of the photosensitive resin composition of the first aspect. When it is in the above range, it tends to easily obtain a balance between sensitivity, developability, and resolution.

The photopolymerization initiator in the photosensitive resin composition of the first aspect is not particularly limited, and a conventionally known photopolymerization initiator can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl). Ethoxy)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-diphenylethane-1-one , bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)- 9H-carbazol-3-yl], 1-(o-ethylindenyl), 2,4,6-trimethylbenzylindenyldiphenylphosphine oxide, 4-benzylindolyl-4'-A Methyl dimethyl sulfide, 4-dimethylamino benzoic acid, methyl 4-dimethylamino benzoate, ethyl 4-dimethylamino benzoate, 4-dimethylamino benzoic acid Butyl ester, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxy Acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, methyl o-benzyl benzoate, 2,4 -Diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxene 2,4-Diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2, 3-diphenylfluorene, azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2 -(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2- (o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-A Oxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-double Dimethylaminobenzophenone (ie, Mie's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethyl methyl ketone), 4, 4'-di Chlorobenzophenone, 3, 3-dimethyl-4-methoxybenzophenone, diphenylethylenedione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzene Amaranth-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-butyl trichloride Acetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthiophene Tons of ketone, dibenzoxyl ketone, pentyl-4-dimethylammonium benzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-double -(9-acridinyl)penta Alkane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-parade(trichloromethyl)-s-triazine, 2-methyl-4 ,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s- Triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino)- 2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4 ,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4- Ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6 -(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl- S-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. Among these, the use of a lanthanide photopolymerization initiator is particularly preferable in terms of sensitivity. Further preferably, an oxime ester compound described later can also be used. These photopolymerization initiators can be used alone or in combination of two or more.

A suitable compound of the oxime ester compound is represented by the following formula (d11).

In the above formula (d11), R ^D13 represents an alkyl group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. X1 is 0 or 1. R ^D14 represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. R ^D15 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.

When R ^D13 is an alkyl group having 1 to 10 carbon atoms, the alkyl group may be a straight chain or a branched chain. In this case, the number of carbon atoms of the alkyl group is preferably from 1 to 8, more preferably from 1 to 5.

When R ^D13 is a phenyl group which may have a substituent, the kind of the substituent is not particularly limited ^insofar as it does not inhibit the object of the present invention. Suitable examples of the substituent which the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic decyloxy group, and may have a phenyl group of a substituent, a phenoxy group which may have a substituent, a benzinyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzhydryloxy group which may have a substituent, and a benzene which may have a substituent An alkyl group, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an amine group, an amine group which may be substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazine-1- Base, halogen, nitro, and cyano. R ^D13 is a phenyl group which may have a substituent, and when a phenyl group has a plurality of substituents, a plurality of substituents may be the same or different.

When the substituent of the phenyl group is an alkyl group, the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6, particularly preferably from 1 to 3, most preferably 1. Further, the alkyl group may be a straight chain or a branched chain. Specific examples of the substituent of the phenyl group are an alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n- Sulfhydryl, isodecyl, n-fluorenyl, and isodecyl. Further, the alkyl group may have an ether bond (-O-) in the carbon chain. In this case, examples of the substituent of the phenyl group include an alkoxyalkyl group and an alkoxyalkoxyalkyl group. When the substituent of the phenyl group is an alkoxyalkyl group, it is preferably a group represented by -R ^D16 -OR ^D17 . R ^D16 is a C 1 to 10 carbon atom which may be a straight chain or a branched chain. R ^D17 is an alkyl group which may be a straight chain or a branched chain having 1 to 10 carbon atoms. The number of carbon atoms of R ^D16 is preferably from 1 to 8, more preferably from 1 to 5, particularly preferably from 1 to 3. The number of carbon atoms of R ^D17 is preferably from 1 to 8, more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxyethoxy group. Ethyl, methoxypropyl and the like.

When the substituent of the phenyl group is an alkoxy group, the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 6. Further, the alkoxy group may be a straight chain or a branched chain. Specific examples of the substituent of the phenyl group which is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec- Butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy , isooctyloxy, sec-octyloxy, tert-octyloxy, n- Alkoxy, isodecyloxy, n-decyloxy, isodecyloxy and the like. Further, the alkoxy group may have an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, 2-methoxy-1-methylethoxy group, and methoxyethoxy group B. An oxy group, an ethoxyethoxyethoxy group, a propoxyethoxyethoxy group, a methoxypropoxy group or the like.

When the substituent of the phenyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the substituent of the phenyl group are a cycloalkyl group, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the substituent of the phenyl group being a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. .

When the substituent of the phenyl group is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where the substituent of the phenyl group is a saturated aliphatic fluorenyl group include an ethyl hydrazino group, a propyl fluorenyl group, an n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, an n-pentamethylene group, and 2,2- Dimethylpropanyl, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodedecyl, n -Tridecyl, n-tetradecyl, n-nonyldecyl, and n-hexadecanyl. Specific examples of the case where the substituent of the phenyl group is a saturated aliphatic decyloxy group include an ethoxy group, a propenyloxy group, an n-butenyloxy group, a 2-methylpropoxy group, and an n-pentyl group. Alkoxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy , n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, and n-hexadecyloxy .

When the substituent of the phenyl group is an alkoxycarbonyl group, the number of carbon atoms is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where the substituent of the phenyl group is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a different one. Butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxy Carbocarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, An n-methoxycarbonyl group, an isodecyloxycarbonyl group or the like.

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

When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group is a single ring of 5 or 6 members containing one or more of N, S, O, or the single ring or the single ring and A heterocyclic group obtained by condensation of a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic ring constituting the heterocyclic group may, for example, be furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole or isothiazide. Azole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, anthraquinone, isoindole, wipes, benzimidazole, benzotriazole, benzoxazole Oxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quinazoline, pyridazine, octyl phenyl, and quinoxaline. When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group may further have a substituent.

When the substituent of the phenyl group is an amine group substituted with 1 or 2 organic groups, a suitable example of the organic group may, for example, be an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, a saturated aliphatic decyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzinyl group which may have a substituent, and a substituent group a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic ring Base. Specific examples of such suitable organic groups include the same substituents as those of the above phenyl group. Specific examples of the amine group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, and different Propylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n- Merylamino, n-decylamino, phenylamino, naphthylamino, ethionylamino, propylamino, n-butylamino, n-pentylamino, n- Hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzhydrylamine, α-naphthylmethylamino, β-naphthylmethylamine And N-ethinyl-N-acetoxyamino group and the like.

a phenyl group, a naphthyl group, or a phenyl group contained in the substituent of the phenyl group And the substituent in the case where the heterocyclic group further has a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, and carbon. An alkoxycarbonyl group having 2 to 7 atomic atoms, a saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, having a carbon number of 1 to 6 Alkyl dialkylamino, morpholin-1-yl, piperazin-1-yl, halogen, nitro, and cyano. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the phenyl group further have a substituent, the number of the substituents is not limited insofar as it does not inhibit the object of the present invention, but is preferably It is 1~4. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the phenyl group have a plurality of substituents, the plurality of substituents may be the same or different.

The substituents in the case where R ^D13 is a phenyl group which may have a substituent are described above, and among these substituents, an alkyl group or an alkoxyalkyl group is preferred.

When R ^D13 is a phenyl group which may have a substituent, the number of the substituent groups and the bonding position with the substituent are not particularly limited insofar as they do not inhibit the object of the present invention. When R ^D13 is a phenyl group which may have a substituent, the phenyl group which may have a substituent, and the o-tolyl group which may have a substituent, is preferable from the viewpoint that the production efficiency of the base is excellent.

When R ^D13 is a carbazole group which may have a substituent, the kind of the substituent is not particularly limited ^insofar as it does not inhibit the object of the present invention. Examples of the carbazole which may be a suitable substituent on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a saturated aliphatic fluorenyl 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 phenylcarbonyl group which may have a substituent, a benzinyl group which may have a substituent, may have a substituent a phenoxycarbonyl group, a benzyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, A naphthylcarbonyl group having a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent, and a carbon atom number which may have a substituent of 11 to 20 a naphthylalkyl group, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group, substituted with 1 or 2 organic groups Amino, morpholin-1-yl, and piperazin-1-yl, halogen, nitro, and cyano.

When R ^D13 is a carbazole group which may have a substituent, the carbazole may be an example of a suitable substituent which may be contained on a nitrogen atom, and examples thereof include an alkyl group having 1 to 20 carbon atoms and a cycloalkane having 3 to 10 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzinyl group which may have a substituent, and a benzene which may have a substituent An oxycarbonyl group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, A naphthylalkyl group having 11 to 20 carbon atoms having a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group is preferable.

Specific examples of the substituent which the carbazolyl group may have, with respect to an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic decyloxy group, may have a substitution a phenylalkyl group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with 1 or 2 organic groups, and a benzene which may have a substituent with R ^D13 Examples of the substituent of the phenyl group in the base group are the same.

In R ^D13 , examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; Alkoxy group having 1 to 6 atomic number; saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic decyloxy group having 2 to 7 carbon atoms; a naphthyl group; a benzindenyl group; a naphthylmethyl group; a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a substituted benzinyl 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; morpholin-1-yl; piperazine- 1-yl; halogen; nitro; cyano. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the carbazolyl group further have a substituent, the number of the substituents is not limited insofar as it does not inhibit the object of the present invention, but Good for 1~4. When the phenyl group, the naphthyl group, and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^D14 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent.

When R ^D14 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, the alkyl group may be a straight chain or a branched chain. In this case, the number of carbon atoms of the alkyl group is preferably from 1 to 8, more preferably from 1 to 5.

The substituent of the alkyl group, the phenyl group or the oxazolyl group in R ^D14 is not particularly limited insofar as it does not inhibit the object of the present invention.

Examples of the substituent which the alkyl group may have on the carbon atom include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkoxy group having 3 to 10 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic decyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, or a phenoxy group of a substituent, a phenylthio group which may have a substituent, a benzinyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzhydryloxy group which may have a substituent, may have a substituent a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, or a naphthylmethoxycarbonyl group having a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group, 1 or 2 organic-substituted amino groups, morpholin-1-yl, and piperazin-1-yl, halogen, nitro, and cyano groups, and the like.

Examples of the phenyl group and the oxazole which are suitable substituents on the carbon atom, and examples thereof include the above-exemplified substituents as the substituent which the alkyl group may have on the carbon atom, and the number of carbon atoms is 1 ~20 alkyl.

Specific examples of the substituent which the alkyl group, the phenyl group or the oxazolyl group may have, with respect to an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic group a decyloxy group, a phenylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with 1 or 2 organic groups, and R ^D13 Examples of the substituent of the phenyl group which is a phenyl group which may have a substituent are the same.

In R ^D14 , examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclic group which are contained in the substituent of the alkyl group, the phenyl group or the carbazolyl group further have a substituent include a carbon number of 1 Alkyl group of ~6; alkoxy group having 1 to 6 carbon atoms; saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturation of 2 to 7 carbon atoms Aliphatic oxime; phenyl; naphthyl; benzhydryl; naphthylmethyl; selected from alkyl having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and benzene a benzinyl group substituted with a group of a 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; piperazin-1-yl; halogen; nitro; cyano. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the alkyl group or the phenyl group further have a substituent, the number of the substituents is not limited insofar as it does not inhibit the object of the present invention. However, it is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

From the viewpoint of the alkali production efficiency of the compound represented by the formula (d11), R ^{D14 is} preferably the following formula (d12): The base of expression, and the following formula (d13): The base of expression.

In the formula (d12), R ^D18 and R ^D19 are each a monovalent organic group, and y1 is 0 or 1. In the formula (d13), R ^D20 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, and A is S or O, and y2 is an integer of 0 to 4.

R ^D18 in the formula (d12) can be selected from various organic groups within the range not inhibiting the object of the present invention. Suitable examples of R ^D18 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. An alkoxycarbonyl group, a phenyl group which may have a substituent, a benzinyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, A naphthyl group having a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group which may have a substituent a cyclic group, a heterocyclic carbonyl group which may have a substituent, and the like.

Among R ^D18 , an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group is preferable.

R ^D19 in the formula (d12) is not particularly limited ^insofar as it does not hinder the object of the present invention, and may be selected from various organic groups. Specific examples of the suitable group of R ^D19 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 heterocyclic group which may have a substituent. Among these, R ^{D19 is more} preferably a phenyl group which may have a substituent, and a naphthyl group which may have a substituent; particularly preferably a 2-methylphenyl group and a naphthyl group.

The substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D18 or R ^D19 further have a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic decyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms A monoalkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D18 or R ^D19 further have a substituent, the number of the substituents is not limited insofar as it does not inhibit the object of the present invention, but is preferably 1 ~4. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D18 or R ^D19 have a plurality of substituents, the plurality of substituents may be the same or different.

When R ^D20 in the formula (d13) is an organic group, R ^D20 may be selected from various organic groups within a range not inhibiting the object of the present invention. Examples of suitable examples when R ^D20 is an organic group in the formula (d13) include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic group having 2 to 7 carbon atoms. Alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic methoxy group having 2 to 7 carbon atoms; phenyl; naphthyl group; benzinyl group; naphthylmethyl group; a group of a group consisting of an alkyl group of ~6, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamine having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; nitro; cyano; 2-methylphenylcarbonyl; -(piperazin-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Among R ^D20 , a benzindenyl group; a naphthylmethyl group; a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Group-substituted benzylidene; nitro; more preferably benzhydryl; naphthylmethyl; 2-methylphenylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; 4-(benzene Phenylcarbonyl.

Further, in the formula (d13), y2 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1. is y2 1, R ^D20 of the bonding position, preferably with respect to the bonded phenyl and R ^D20 bonded portion bonded to the sulfur atom of the para position.

R ^D15 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. When it is a phenyl group which may have a substituent, the phenyl group may have a substituent which is the same as when R ^D13 is a phenyl group which may have a substituent. As R ^D15 , a methyl group, an ethyl group or a phenyl group is preferred; a methyl group or a phenyl group is more preferred.

The oxime ester compound represented by the above formula (d11), when x1 is 0, can be synthesized, for example, by the method described below. First, a ketone compound represented by R ^D14 -CO-R ^{D13 is deuterated} by hydroxylamine to obtain an ^anthracene compound represented by R ^D14 -(C=N-OH)-R ^D13 . Next, the obtained hydrazine compound is ^thiolated by an acid halide represented by R ^D15 -CO-Hal (Hal represents halogen) or an acid anhydride represented by (R ^D15 CO) ₂ O to obtain the above formula wherein x1 is 0. (d11) represents an oxime ester compound.

Further, the oxime ester compound represented by the above formula (d11), when x1 is 1, can be synthesized, for example, by the method described below. First, a ketone compound represented by R ^D14 -CO-CH ₂ -R ^D13 is reacted with a nitrite in the presence of hydrochloric acid to obtain a ^hydrazine compound represented by R ^D14 -CO-(C=N-OH)-R ^D13 . Next, the obtained hydrazine compound is ^thiolated by an acid halide represented by R ^D15 -CO-Hal (Hal represents halogen) or an acid anhydride represented by (R ^D15 CO) ₂ O to obtain the above formula wherein x1 is 1. (d11) represents an oxime ester compound.

The compound represented by the above formula (d11) includes a compound represented by the following formula (d14).

In the above formula (d14), x1 and R ^D14 are as described above. R ^D21 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, and x 2 is an integer of 0 to 4, and R ^D22 is a hydrogen atom or an alkane having 1 to 6 carbon atoms. base.

In the above formula (d14), R ^D21 is not particularly limited as long as it does not inhibit the object of the present invention, and is an organic group, and is appropriately selected from various organic groups. Suitable examples of R ^D21 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic decyloxy group, and a phenyl group which may have a substituent. a phenoxy group which may have a substituent, a benzindenyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, and A naphthyl group having a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent, may have a substitution a naphthylalkyl group, a heterocyclic group which may have a substituent, an amine group, an amine group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, And cyano and the like. When x2 is an integer of 2 to 4, R ^D21 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent which the substituent further has.

When R ^D21 is an alkyl group, it preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. Further, when R ^D21 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^D21 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl. , isoamyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-fluorenyl, isoindole Base, n-fluorenyl, and isodecyl. Further, when R ^D21 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxyethoxy group. Ethyl ethyl, methoxypropyl and the like.

When R ^D21 is an alkoxy group, it preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. Further, when R ^D21 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^D21 is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert. -butoxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy And sec-octyloxy, tert-octyloxy, n-decyloxy, isodecyloxy, n-decyloxy, and isodecyloxy. Further, when R ^D21 is an alkoxy group, the alkoxy group may further contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Propoxyethoxyethoxy, methoxypropoxy and the like.

When R ^D21 is a cycloalkyl group or a cycloalkoxy group, it preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. Specific examples of the case where R ^D21 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 of the case where R ^D21 is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^D21 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^D21 is a saturated aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, an n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, an n-pentamethylene group, and a 2,2-dimethyl propyl hydrazine group. Base, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodedecyl, n-tridecyl , n-tetradecyl, n-pentadecanyl, and n-hexadecanyl. Specific examples of the case where R ^D21 is a saturated aliphatic oxime group include an ethoxy group, a propenyloxy group, an n-butenyloxy group, a 2-methylpropenyloxy group, an n-pentyloxy group, and 2 ,2-dimethylpropoxycarbonyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-eleven An alkoxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, and an n-hexadecanoyloxy group.

When R ^D21 is an alkoxycarbonyl group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^D21 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, and the like. Sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n- Heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, n-decyloxy A carbonyl group, an isodecyloxycarbonyl group or the like.

When R ^D21 is a phenylalkyl group, it preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. Further, when R ^D21 is a naphthylalkyl group, it preferably has 11 to 20 carbon atoms, more preferably 11 to 14 carbon atoms. Specific examples of the case where R ^D21 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^D21 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. . When R ^D21 is a phenylalkyl group or a naphthylalkyl group, R ^D21 may further have a substituent on the phenyl group or the naphthyl group.

When R ^D21 is a heterocyclic group, the heterocyclic group is a monocyclic ring of 5 or 6 members including one or more of N, S, and O, or a condensation of the monocyclic ring or the monocyclic ring with a benzene ring. Heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic ring constituting the heterocyclic group may, for example, be furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine or pyridazine. , benzofuran, benzothiophene, anthracene, isoindole, wipes, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quin Oxazoline, pyridazine, octyl phenyl, and quinoxaline. When R ^D21 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^D21 is an amine group substituted with one or two organic groups, a suitable example of the organic group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 carbon atoms. a saturated aliphatic fluorenyl group of -20, a phenyl group which may have a substituent, a benzinyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a naphthyl group which may have a substituent And a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such suitable organic groups are the same as R ^D21 . Specific examples of the amine group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, and different Propylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n- Merylamino, n-decylamino, phenylamino, naphthylamino, ethionylamino, propylamino, n-butylamino, n-pentylamino, n- Hexylamino group, n-heptylamino group, n-octylamino group, n-decylamino group, benzhydrylamino group, α-naphthylmethylamino group, and β-naphthylmethyl group Amine and the like.

The substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D21 further have a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms, and a monoalkyl group having an alkyl group having 1 to 6 carbon atoms An amino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D21 further have a substituent, the number of the substituents is not limited insofar as it does not inhibit the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D21 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the R ^D21 , it is preferably selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, which is chemically stable or has few steric hindrance and easy synthesis of an oxime ester compound. And a group of a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; more preferably an alkyl group having 1 to 6 carbon atoms; particularly preferably a methyl group.

R ^{D21 is} bonded to the phenyl group, and when the phenyl group bonded to R ^D21 is bonded to the main skeleton of the phenyl group and the oxime ester compound at a position of 1 position and the position of the methyl group is 2 positions, It is preferably 4 bits or 5 bits; more preferably 5 bits. Further, x2 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1.

R ^D22 in the above formula (d14) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^D22 , a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

Specific examples of particularly suitable compounds as the oxime ester compound are shown below.

The compound represented by the following formula (d15) is also suitably used as the oxime ester compound.

(R ^D23 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^D24 and R ^D25 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 ^D24 and R ^D25 may also be bonded to each other to form a ring, R ^D26 is a monovalent organic group, R ^D27 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and x4 is An integer from 0 to 4, with x3 being 0 or 1).

In the formula (d15), R ^D23 is a hydrogen atom, a nitro group or a monovalent organic group. R ^D23 is attached to the anthracene ring of the formula (d15) and bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) _x3 -. In the formula (d15), R ^D23 is not particularly limited to the bonding position of the anthracene ring. When the compound represented by the formula (d15) has one or more R ^D23 , the synthesis of the compound represented by the formula (d15) is easy, etc., and preferably one of the R ^D23 is bonded to the anthracene ring. 2 digits. When R ^D23 is plural, a plurality of R ^D23 may be the same or different.

When R ^D23 is an organic group, R ^D23 is not particularly limited as long as it does not inhibit the object of the present invention, and is appropriately selected from various organic groups. Suitable examples of the case where R ^D23 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyloxy group, and may have a substitution. a phenyl group, a phenoxy group which may have a substituent, a benzinyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyloxy group which may have a substituent, a phenyl group which may have a substituent An alkyl group, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and Piperazine-1-yl and the like.

When R ^D23 is an alkyl group, the number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. Further, when R ^D23 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^D23 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, and n-pentyl group. , isoamyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-fluorenyl, isoindole Base, n-fluorenyl, and isodecyl. Further, when R ^D23 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxyethoxy group. Ethyl ethyl, methoxypropyl and the like.

When R ^D23 is an alkoxy group, the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. Further, when R ^D23 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^D23 is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert. -butoxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy And scc-octyloxy, tert-octyloxy, n-decyloxy, isodecyloxy, n-decyloxy, and isodecyloxy. Further, when R ^D23 is an alkoxy group, the alkoxy group may further contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Propoxyethoxyethoxy, methoxypropoxy and the like.

When R ^D23 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^D23 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 of the case where R ^D23 is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^D23 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms of the saturated aliphatic fluorenyl group or the saturated aliphatic fluorenyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of the case where R ^D23 is a saturated aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, an n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, an n-pentamethylene group, and a 2,2-dimethyl propyl hydrazine group. Base, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodedecyl, n-tridecyl , n-tetradecyl, n-pentadecanyl, and n-hexadecanyl. Specific examples of the case where R ^D23 is a saturated aliphatic decyloxy group include an ethoxycarbonyl group, a propenyloxy group, an n-butenyloxy group, a 2-methylpropenyloxy group, an n-pentyloxy group, and 2 ,2-dimethylpropoxycarbonyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-eleven An alkoxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, and an n-hexadecyloxy group.

When R ^D23 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where R ^D23 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, and the like. See-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n- Heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, n-decyloxy A carbonyl group, an isodecyloxycarbonyl group or the like.

When R ^D23 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. Further, when R ^D23 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R ^D23 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^D23 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. . When R ^D23 is a phenylalkyl group or a naphthylalkyl group, R ^D23 may further have a substituent on the phenyl group or the naphthyl group.

When R ^D23 is a heterocyclic group, the heterocyclic group is a monocyclic ring of 5 or 6 members including one or more of N, S, and O, or a condensation of the monocyclic ring or the monocyclic ring with a benzene ring. Heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. The heterocyclic ring constituting the heterocyclic group may, for example, be furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine or pyridazine. , benzofuran, benzothiophene, anthracene, isoindole, wipes, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quin Oxazoline, pyridazine, octyl phenyl, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ^D23 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^D23 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when R ^D23 is a heterocyclic group.

When R ^D23 is an amine group substituted with one or two organic groups, a suitable example of the organic group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 carbon atoms. a saturated aliphatic fluorenyl group of ~21, a phenyl group which may have a substituent, a benzinyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a naphthyl group which may have a substituent And a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such suitable organic groups are the same as R ^D23 . Specific examples of the amine group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, and different Propylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n- Merylamino, n-decylamino, phenylamino, naphthylamino, ethionylamino, propylamino, n-butylamino, n-pentylamino, n- Hexylamino group, n-heptylamino group, n-octylamino group, n-decylamino group, benzhydrylamino group, α-naphthylmethylamino group, and β-naphthylmethyl group Amine and the like.

The substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D23 further have a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms, and a monoalkyl group having an alkyl group having 1 to 6 carbon atoms An amino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D23 further have a substituent, the number of the substituents is not limited insofar as it does not inhibit the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^D23 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the above-mentioned examples, R ^{D23 is} preferably a nitro group or a group represented by R ^D28 -CO-, and has a tendency to improve sensitivity. R ^D28 is not particularly limited ^insofar as it does not hinder the object of the present invention, and may be selected from various organic groups. Examples of a suitable group of R ^D28 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 heterocyclic group which may have a substituent. As R ^D28 , among these, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable.

Further, when R ^D23 is a hydrogen atom, the transparency tends to be good, and it is preferable to form a film of a cured film which requires transparency. Further, when R ^D23 is a hydrogen atom and R ^D26 is a group represented by the formula (R4-2) described later, the transparency tends to be further improved.

In the formula (d15), R ^D24 and R ^D25 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 ^D24 and R ^D25 may also be bonded to each other to form a ring. Among these, R ^D24 and R ^{D25 are} preferably a chain alkyl group which may have a substituent. When R ^D24 and R ^D25 are a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ^D24 and R ^D25 are a chain-like alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 6. Specific examples of the case where R ^D24 and R ^D25 are a chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. , n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n- Sulfhydryl, isodecyl, n-fluorenyl, and isodecyl. Further, when R ^D24 and R ^D25 are alkyl groups, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxyethoxy group. Ethyl ethyl, methoxypropyl and the like.

When R ^D24 and R ^D25 are a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.

The alkyl group may have a substituent, and is not particularly limited insofar as it does not hinder the object of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the cycloalkyl group are the same as those suitable for the case where R ^D23 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. Specific examples of the heterocyclic group are the same as those suitable for the case where R ^D23 is a heterocyclic group. When R ^D23 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The alkoxy group contained in the alkoxycarbonyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

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

When R ^D24 and R ^D25 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. When R ^D24 and R ^D25 are a cyclic organic group, the cyclic organic group may have a substituent which is the same as when R ^D24 and R ^D25 are a chain alkyl group.

When R ^D24 and R ^D25 are an aromatic hydrocarbon group, 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 a plurality of benzene ring bonds or condensations, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 The following is particularly good. Specific preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.

When R ^D24 and R ^D25 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decyl group, an isodecyl group, a tricyclodecyl group, and a tricyclic ring. Mercapto, tetracyclododecyl, and adamantyl.

When R ^D24 and R ^D25 are a heterocyclic group, the heterocyclic group is a single ring of 5 or 6 members containing one or more of N, S, O, or the single ring or the monocyclic ring is condensed with the benzene ring. And the resulting heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. The heterocyclic ring constituting the heterocyclic group may, for example, be furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine or pyridazine. , benzofuran, benzothiophene, anthracene, isoindole, wipes, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quin Oxazoline, pyridazine, octyl phenyl, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

R ^D24 and R ^D25 may also be bonded to each other to form a ring. The group consisting of a ring formed by R ^D24 and R ^{D25 is} preferably a cycloalkylene group. When R ^D24 is bonded to R ^D25 to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to 6-membered ring, more preferably a 5-membered ring.

When the group formed by the bonding of R ^D24 and R ^D25 is a cycloalkylene group, the cycloalkylene group may also be condensed with one or more other rings. Examples of the ring which can be condensed with the cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, and a thiophene ring. , pyrrole ring, pyridine ring, pyrazine ring, and pyrimidine ring.

Examples of the base particularly suitable for R ^D24 and R ^D25 described above include a group represented by the formula -A ^D1 -A ^D2 . In the formula, A ^D1 is a linear alkylene group, and A ^D2 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 of the linear alkyl group of ^{D D1} is preferably from 1 to 10, more preferably from 1 to 6. When A ^D2 is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably from 1 to 10, more preferably from 1 to 6. When A ^D2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; more preferably a fluorine atom, a chlorine atom or a bromine atom. When A ^D2 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; more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ^D2 is a cyclic organic group, the cyclic organic group is the same as the cyclic organic group which has a substituent as R ^D24 and R ^D25 . When A ^D2 is an alkoxycarbonyl group, the alkoxycarbonyl group is the same as the alkoxycarbonyl group which has a substituent as R ^D24 and R ^D25 .

Specific examples of suitable R ^D24 and R ^D25 include an alkyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; Ethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy Base-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5- Alkoxyalkyl group such as ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; - cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano- N-heptyl, and cyanoalkyl such as 8-cyano-n-octyl; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5 Phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl phenylalkyl; 2-cyclohexyl , 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl , 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n- a cycloalkyl group such as 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl Alkyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6- Methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n -propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl And an alkoxycarbonylalkyl group such as 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro- N-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo- N-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl And a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

As R ^D24 and R ^D25 , particularly suitable among the above, ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2 -phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3, 4,4,5,5,5-heptafluoro-n-pentyl.

Examples of a suitable organic group of R ^D26 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, or a saturated aliphatic ^oxime, similarly to R ^{D23 .} a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzinyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyloxy group which may have a substituent, may have a phenylalkyl group of a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl fluorenyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, may have a substituent Naphthylmethoxycarbonyl, naphthylalkyl group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl group which may have a substituent, amine group substituted by 1 or 2 organic groups, morpholine- 1-yl, piperazin-1-yl and the like. Specific examples of these are the same as those described for R ^D23 . Further, as R ^D26 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring is also preferable. The phenoxyalkyl group and the phenylthioalkyl group may have a substituent which is the same as the substituent which the phenyl group contained in R ^D23 may have.

Among the organic groups, R ^{D26 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. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably from 1 to 8, more preferably from 1 to 4, particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferred.

Further, as R ^D26 , it is also preferably a group represented by -A ^D3 -CO-OA ^D4 . A ^D3 is a divalent organic group, preferably a divalent hydrocarbon group, more preferably an alkylene group. A ^D4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ^D3 is an alkylene group, the alkyl group may be linear or branched, preferably linear. When A ^D3 is an alkyl group, the number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 4.

Suitable examples of A ^D4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific examples of suitable A ^D4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n. a hexyl group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.

Specific examples of suitable groups of -A ^D3 -CO-OA ^D4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2- N-Butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3 -methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl , 3- n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n -propyl and the like.

Above described R ^D26, as R ^D26, is preferably represented by the following formula (R4-1) or (R4-2) represents the group.

(In the formulae (R4-1) and (R4-2), R ^D29 and R ^D30 are each an organic group, z1 is an integer of 0 to 4, and R ^D29 and R ^D30 are present at an adjacent position on the benzene ring. R ^D29 and R ^D30 may also be bonded to each other to form a ring, z2 is an integer from 1 to 8, z3 is an integer from 1 to 5, z4 is an integer from 0 to (r+3), and R ⁹ is an organic group).

Examples of the organic group of R ^D29 and R ^D30 in the formula (R4-1) are the same as those of R ^D23 . As R ^D29 , an alkyl group or a phenyl group is preferred. When R ^D29 is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. In other words, R ^{D29 is} most preferably a methyl group. When R ^D29 is bonded to R ^D30 to form a ring, the ring may be an aromatic ring or an aliphatic ring. A suitable example of a group represented by the formula (R4-1) and a group in which R ^D29 and R ^D30 form a ring may, for example, be a naphthalen-1-yl group or a 1,2,3,4-tetrahydronaphthalen-5-yl group. Wait. In the above formula (R4-1), z1 is an integer of 0 to 4, preferably 0 or 1, more preferably 0.

In the above formula (R4-2), R ⁹ is an organic group. The organic group is the same as the organic group described for R ^D23 . Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3. As R ⁹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or the like is preferably exemplified, and among these, a methyl group is more preferable.

In the above formula (R4-2), z3 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (R4-2), z4 is 0 to (z3+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (R4-2), z2 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, particularly preferably 1 or 2.

In the formula (d15), R ^D27 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. When v is a substituent which may be an alkyl group, a phenyl group, a naphthyl group, etc. are preferable. Further, when R ^D23 is an aryl group, it may have a substituent, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom or the like is preferably exemplified.

In the formula (d15), as R ^D27 , 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 are preferably exemplified. Etc. Among them, methyl or phenyl is more preferred.

The method for producing the compound represented by the formula (d15) is not particularly limited. The compound represented by the formula (d15) is preferably a step of converting the thiol group (=N-OH) contained in the compound represented by the following formula (d16) to the oxime ester group represented by =NO-COR ^D27 . Method to manufacture. R ^D27 is the same as R ^D27 in formula (d15).

(R ^D23 , R ^D24 , R ^D25 , R ^D26 , x3 , and x4 are the same as equation (d15). x4 is an integer from 0 to 4, and x3 is 0 or 1).

Therefore, the compound represented by the above formula (d16) is an intermediate for synthesis which is a compound represented by the formula (d15).

The method of converting the thiol group (=N-OH) to the oxime ester group represented by =NO-COR ^D27 is not particularly limited. Typically, a method of reacting a thiolating agent imparting a mercapto group represented by -COR ^D27 with a hydroxyl group in a mercapto group is exemplified. Examples of the thiolating agent include an acid anhydride represented by (R ^D27 CO) ₂ O or an acid halide represented by R ^D27 COHal (Hal is a halogen atom).

The compound represented by the formula (d15), when x3 is 0, can be synthesized, for example, in accordance with the following Scheme 1. In the scheme 1, an anthracene derivative represented by the following formula (d1-1) is used as a raw material. When R ^D23 is a nitro group or a monovalent organic group, the anthracene derivative represented by the formula (d1-1) can be introduced into the anthracene derivative substituted with R ^D24 and R ^D25 at the 9 position by a well-known method. Obtained by ^D23 . The anthracene derivative substituted with R ^D24 and R ^{D25 in the} 9th position, for example, when R ^D24 and R ^D25 are alkyl groups, can be as described in JP-A-06-234668, in the presence of an alkali metal hydroxide. It is obtained by reacting hydrazine with an alkylating agent in an aprotic polar organic solvent. Further, an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and an interphase transfer catalyst such as tetrabutylammonium iodide or tert-butoxide may be added to the organic solvent solution of cerium. The alkylation reaction is carried out to obtain a 9,9-alkyl substituted anthracene.

The thiol group represented by -CO-R ^D26 is introduced into the anthracene derivative represented by the formula (d1-1) by a Friedel-Crafts thiolation reaction, and the formula (d1-3) is obtained. Represents a cockroach derivative. The thiolating agent for introducing a mercapto group represented by -CO-R ^D26 may be a halogenated carbonyl compound or an acid anhydride. As the thiolation agent, a halocarbonyl compound represented by the formula (d1-2) is preferred. In the formula (d1-2), Hal is a halogen atom. The position at which the sulfhydryl group is introduced on the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Kraft reaction or by protecting and deprotecting other positions at the thiolated position.

Next, the group represented by -CO-R ^D26 in the anthracene derivative represented by the obtained formula (d1-3) is converted into a group represented by -C(=N-OH)-R ^{D26 to} give a formula (d1- 4) Representation of the ruthenium compound. The method of converting the group represented by -CO-R ^{D26 to} a group represented by -C(=N-OH)-R ^D26 is not particularly limited, and is preferably deuterated by hydroxylamine. An anthracene compound of the formula (d1-4), an acid anhydride represented by the following formula (d1-5) ((R ^D27 CO) ₂ O), or an acid halide represented by the following formula (d1-6) (R ^D27) The reaction of COHal and Hal is a halogen atom), and a compound represented by the following formula (d1-7) is obtained.

Further, in the formulas (d1-1), (d1-2), (d1-3), (d1-4), (d1-5), (d1-6), and (d1-7), R ^D23 , R ^D24 , R ^D25 , R ^D26 , and R ^D27 , are the same as formula (d15).

Further, in the scheme 1, R ^D26 contained in each of the formula (d1-2), the formula (d1-3), and the formula (d1-4) may be the same or different. In other words, R ^D26 in the formula (d1-2), the formula (d1-3), and the formula (d1-4) may be chemically modified in the synthesis process shown in the scheme 1. Examples of the chemical modification include esterification, etherification, thiolation, guanidation, halogenation, and substitution of a hydrogen atom in an amine group with an organic group. The chemical modification that R ^D26 can be subjected to is not limited to this.

<Process 1>

The compound represented by the formula (d15), when x3 is 1, can be synthesized, for example, in accordance with the following Scheme 2. In the scheme 2, an anthracene derivative represented by the following formula (d1-7) is used as a raw material. The anthracene derivative represented by the formula (d2-1) is introduced into the -CO-CH ₂ -R by the compound represented by the formula (d1-1) by the Friedel-Zafft reaction by the same method as in the first scheme. ^D26 is obtained from the base. As the thiolating agent, a carboxylic acid halide represented by the formula (d1-8): Hal-CO-CH ₂ -R ^D26 is preferred. Next, a methylene group existing between R ^D26 and a carbonyl group in the compound represented by the formula (d1-7) is deuterated to obtain a ketoxime compound represented by the following formula (d2-3). The method of deuterating the methylene group is not particularly limited, but it is preferably a nitrite represented by the following formula (d2-2) in the presence of hydrochloric acid (RONO, R is an alkyl group having 1 to 6 carbon atoms) The method of carrying out the reaction. Then, the ketone oxime compound represented by the following formula (d2-3), the acid anhydride represented by the following formula (d2-4) ((R ^D27 CO) ₂ O), or the following formula (d2-5) can be represented. The acid halide (R ^D27 COHal, Hal is a halogen atom) is reacted to obtain a compound represented by the following formula (d2-6). Further, in the following formulas (d2-1), (d2-3), (d2-4), (d2-5), and (d2-6), R ^D23 , R ^D24 , R ^D25 , R ^D26 , And R ^D27 , which is the same as formula (d15).

Further, in the scheme 2, R ^D26 contained in each of the formula (d1-8), the formula (d2-1), and the formula (d2-3) may be the same or different. In other words, R ^D26 in the formula (d1-8), the formula (d2-1), and the formula (d2-3) may be chemically modified in the synthesis process shown in the scheme 2. Examples of the chemical modification include esterification, etherification, thiolation, guanidation, halogenation, and substitution of a hydrogen atom in an amine group with an organic group. The chemical modification that R ^D26 can be subjected to is not limited to this.

<Process 2>

Specific examples of suitable compounds represented by the formula (d15) include the following oxime ester compounds.

The content of the photopolymerization initiator is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the solid content of the photosensitive resin composition of the first aspect. When it is in the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved to suppress the curing failure.

The photosensitive resin composition of the first aspect contains the compound represented by the above formula (1) as described above. The compound has good solubility in an organic solvent, and when it is contained in a photosensitive resin composition, good micro patterning properties can be obtained.

The content of the compound represented by the above formula (1) is preferably from 0.5 to 95 parts by mass, more preferably from 1 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. By setting it as the said range, it can obtain favorable microscopic-formation characteristics, and the favorable developability is acquired.

The photosensitive resin composition of the first aspect may further contain a colorant. By containing a coloring agent, for example, a color filter forming use as a liquid crystal display can be preferably used. Further, the photosensitive resin composition of the first aspect can be preferably used as a black matrix in a color filter by using a light-shielding agent as a coloring agent.

The coloring agent is not particularly limited. For example, it is preferably a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), specifically, a color index as described below ( CI) number.

CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, 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, 185; CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same, 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, 73; CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same, but only the number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, but only the number), 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, 265; CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, only the number is described), 2, 15, and 15 : 3, 15:4, 15:6, 16, 22, 60, 64, 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37; C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28; C.I. Pigment Black 1, C.I. Pigment Black 7.

Moreover, when a coloring agent is used as a light shielding agent, it is preferable to use a black pigment as a light shielding agent. Examples of the black pigment include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, metal sulfates, and metal carbonates. Various pigments of organic matter and inorganic matter. Among these, carbon black having a high light-shielding property is particularly preferable.

As the carbon black, a known carbon black such as black, furnace black, hot carbon black or lamp black can be used, and it is preferable to use a groove black having excellent light shielding properties. Further, carbon black may be coated with a resin.

Since the resin is coated with carbon black, the conductivity is low compared to the carbon black which is not coated with the resin. Therefore, when a black matrix of a liquid crystal display is used, it is possible to manufacture a display having low current leakage and high reliability and low power consumption.

Further, in order to adjust the color tone of carbon black, the above-mentioned organic pigment may be appropriately added as an auxiliary pigment.

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

Further, the inorganic pigment and the organic pigment may be used singly or in combination, and when used in combination, relative to the inorganic pigment The organic pigment is preferably used in an amount of from 10 to 80 parts by mass, more preferably from 20 to 40 parts by mass, based on 100 parts by mass of the total of the organic pigment.

The content of the coloring agent may be appropriately determined depending on the use of the photosensitive resin composition of the first aspect, and as an example, compared with 100 parts by mass of the solid content of the photosensitive resin composition of the first aspect. Preferably, it is 5 to 70 parts by mass, more preferably 25 to 60 parts by mass.

In particular, when a black matrix is formed using the photosensitive resin composition of the first aspect, it is preferable to adjust the amount of the light-shielding agent in the photosensitive resin composition so that the OD value per 1 μm of the film thickness of the black matrix is 4 or more. the amount. When the film thickness in the black matrix has 4 or more OD values per 1 μm, it can be used for a black matrix of a liquid crystal display to obtain sufficient display contrast.

Further, the coloring agent is preferably a dispersing agent, and is added to the photosensitive resin composition after being dispersed in an appropriate concentration.

The organic solvent in the photosensitive resin composition of the first aspect may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether or 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 Alcohol 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 (poly)alkylene glycol such as ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Ester, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Alcohol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, a ketone such as cyclohexanone, 2-heptanone or 3-heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionic acid Ethyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate , n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyrate n- Propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate Other esters such as ethyl acetate, ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, An amide such as N,N-dimethylacetamide or the like. These organic solvents may be used alone or in combination of two or more.

Among the above organic solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate, the above-mentioned alkali-soluble resin, the above photopolymerizable monomer, the above photopolymerization initiator, and the above formula ( 1) the compound shown shows excellent solubility and can be colored as described above The dispersibility of the agent is good and preferable; it is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

The content of the organic solvent is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the solid content of the photosensitive resin composition of the first aspect.

The photosensitive resin composition of the first aspect may contain various additives as needed. Examples of the additives include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregating agent, a thermal polymerization inhibiting agent, an antifoaming agent, and a surfactant. Further, 1-(N,N-bis(2-ethylhexyl)amino)methyl-1H-benzotriazole or 1-(N,N-di(2) may be used alone or in combination of two or more. -ethylhexyl)amino)methyl-1H-methylbenzotriazole, carboxybenzotriazole, benzotriazole, methylbenzotriazole, dihydroxypropylbenzotriazole, bisamine A benzotriazole derivative such as methylbenzotriazole or the like is used as an optional additive.

The amount of the additive to be added may be appropriately adjusted in the range of, for example, 0.001% by mass to 10% by mass based on the entire composition, and preferably 0.1 to 5% by mass.

In addition, when the alkali-soluble resin has a carboxyl group, even when the alkali-soluble resin, the compound represented by the above formula (1), and an organic solvent are contained, and the photopolymerizable monomer and the photopolymerization initiator are not contained, The function of the photosensitive resin composition. In other words, when a base is produced by the compound represented by the above formula (1) by electromagnetic wave irradiation or heating, the alkali-soluble resin is dehydrated and condensed by using the base as a catalyst. Thereby, the solubility to the developer is lowered.

In this case, when the photopolymerization initiator is further contained, it is preferred because it promotes the generation of a base from the compound represented by the above formula (1). In other words, when a radical is generated by a photopolymerization initiator by electromagnetic wave irradiation, the compound represented by the above formula (1) is attacked by the radical to promote the generation of a base. Further, by supplementing the radical with a base generated from the compound represented by the above formula (1), the balance of the alkali-generating reaction moves, and a base is further produced. Further, the base produced by the compound represented by the above formula (1) reacts with the compound after the generation of the radical to further promote the generation of the base.

(2) photosensitive resin composition of the second aspect

The photosensitive resin composition of the second aspect is a negative photosensitive property containing an alkali-soluble resin having a phenolic hydroxyl group, an acid crosslinkable substance, a photoacid generator, a compound represented by the above formula (1), and an organic solvent. Resin composition.

In the alkali-soluble resin having a phenolic hydroxyl group in the photosensitive resin composition of the second aspect, for example, a polyhydroxystyrene resin can be used.

The polyhydroxystyrene resin has at least a constituent unit derived from hydroxystyrene.

Here, "hydroxystyrene" means that a hydrogen atom bonded to the α-position of hydroxystyrene and hydroxystyrene is substituted with another substituent such as a halogen atom, an alkyl group or a halogenated alkyl group, and the like. The concept of a hydroxystyrene derivative (monomer) of a derivative.

a "hydroxystyrene derivative" which maintains at least a benzene ring and a hydroxyl group to which it is bonded, for example, a hydrogen atom bonded to the α-position of hydroxystyrene Further substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group, or the like, and a benzene ring bonded to a hydroxyl group of the hydroxystyrene are further bonded with an alkyl group having 1 to 5 carbon atoms. Or one or two hydroxyl groups are further bonded to the benzene ring to which the hydroxyl group is bonded (in this case, the total number of hydroxyl groups is 2 to 3).

The halogen atom may, for example, be a chlorine atom, a fluorine atom or a bromine atom, and is preferably a fluorine atom.

Further, the "α-position of hydroxystyrene" means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The constituent unit derived from hydroxystyrene is represented, for example, by the following formula (b-1).

In the above formula (b-1), R ^b1 represents a hydrogen atom, an alkyl group, a halogen atom or a halogenated alkyl group, R ^b2 represents an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 3, and q represents 0 to 0. An integer of 2.

The alkyl group of R ^b1 is preferably a carbon number of 1 to 5. Further, a linear or branched alkyl group is preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and an isopenic group. Base, neopentyl and so on. Among these, industrially, methyl is preferred.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

The halogenated alkyl group is a part or all of a hydrogen atom of the above alkyl group having 1 to 5 carbon atoms which is substituted by a halogen atom. In particular, it is preferred that all of the hydrogen atoms are replaced by fluorine atoms. Further, it is preferably a linear or branched fluorinated alkyl group; more preferably a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group or the like; and most preferably a trifluoromethyl group ( -CF ₃ ).

R ^{b1 is} preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

The alkyl group having 1 to 5 carbon atoms of R ^b2 may be the same as the case of R ^b1 .

q is an integer from 0 to 2. Among them, 0 or 1 is preferable, and industrially excellent is 0.

The substitution position of R ^b2 may be any of the ortho, meta and para positions when q is 1, and further, when q is 2, any substitution position may be combined.

p is an integer of 1 to 3, preferably 1.

The position of substitution of a hydroxyl group may be any of an ortho, meta or para position when p is 1, but is preferably a para position because it is easily available and low in price. Further, when p is 2 or 3, any substitution position can be combined.

The constituent units represented by the above formula (b-1) may be used alone or in combination of two or more.

In the polyhydroxystyrene resin, the ratio of the constituent unit derived from the hydroxystyrene is preferably 60 to 100 mol%, more preferably 70 to 100, based on the total constituent unit of the polyhydroxystyrene resin. Mole%, and more preferably 80~100 mol%. By becoming within the above range When it is a photosensitive resin composition, moderate alkali solubility can be obtained.

The polyhydroxystyrene resin preferably further has a constituent unit derived from styrene.

Here, the "composition unit derived from styrene" means a constituent unit in which an ethylene double bond containing styrene and a styrene derivative (excluding hydroxystyrene) is cracked.

The "styrene derivative" is a carbon atom in which a hydrogen atom bonded to the α-position of styrene is substituted with a halogen atom, an alkyl group, a halogenated alkyl group or the like, and a hydrogen atom of a phenyl group of styrene. A substituent such as an alkyl group of 1 to 5 is substituted.

The halogen atom may, for example, be a chlorine atom, a fluorine atom or a bromine atom, and is preferably a fluorine atom.

Further, the "alpha position of styrene" means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The constituent unit derived from styrene is represented, for example, by the following formula (b-2). In the formula, R ^b1 , R ^b2 and q have the same meanings as in the above formula (b-1).

R ^b1 and R ^b2, R of the above formula include (b1) of ^b1 and R ^b2 each are the same.

q is an integer from 0 to 2. Of these, 0 or 1 is preferred, and industrially preferred is 0.

The substitution position of R ^b2 may be any of the ortho, meta and para positions when q is 1, and further, when q is 2, any substitution position may be combined.

The constituent units represented by the above formula (b-2) may be used alone or in combination of two or more.

In the polyhydroxystyrene resin, the ratio of the constituent units derived from styrene is preferably 40 mol% or less, more preferably 30 mol% or less, based on the total constituent unit of the polyhydroxystyrene resin. More preferably, it is less than 20% by mole. By setting it as the said range, it is set as the photosensitive resin composition, and the moderate alkali solubility is acquired, and the balance with another structural unit is also favorable.

Further, the polyhydroxystyrene resin may have a constituent unit derived from hydroxystyrene or a constituent unit other than a constituent unit derived from styrene. More preferably, the polyhydroxystyrene resin is a polymer formed only from a constituent unit derived from hydroxystyrene or a copolymer composed of a constituent unit derived from hydroxystyrene and a constituent unit derived from styrene.

The mass average molecular weight of the polyhydroxystyrene resin is not particularly limited, and is preferably 1,500 to 40,000, more preferably 2,000 to 8,000.

Further, an alkali-soluble resin having a phenolic hydroxyl group may also be a novolak resin. The novolak resin can be obtained by addition condensation of a phenol and an aldehyde in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, and the like. Cresols; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-dimethyl Phenomenols such as phenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butyl Alkyl phenols such as phenol, m-butyl phenol, p-butyl phenol, p-tert-butyl phenol, etc.; 2,3,5-trimethylphenol, 3,4,5-trimethylphenol And other trialkylphenols; resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, gallicol, phloroglucinol and other polyphenols; alkyl resorcinol, alkyl An alkyl polyphenol such as a tea phenol or an alkyl hydroquinone (all alkyl groups are carbon atoms 1 to 4); α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A, and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferred; more preferably, m-cresol and P-cresol are used in combination. At this time, by adjusting the blending ratio of the two, various characteristics such as sensitivity can be adjusted.

Examples of the aldehydes include formaldehyde, p-formaldehyde, furaldehyde, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes may be used alone or in combination of two or more.

Examples of the acid catalyst 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, diethylsulfonic acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

Specific examples of the novolac resin thus obtained include a phenol/formaldehyde condensed novolak resin, a cresol/formaldehyde condensed novolac resin, a phenol-naphthol/formaldehyde condensed novolac resin, and the like.

The mass average molecular weight of the novolak resin, no special The limit is preferably from 1,000 to 30,000, more preferably from 3,000 to 25,000.

Further, as the alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylene glycol condensation resin, a cresol-xylene glycol condensation resin, a phenol-dicyclopentadiene condensation resin, or the like may be used.

The content of the alkali-soluble resin having a phenolic hydroxyl group is preferably from 20 to 80% by mass, and more preferably from 35 to 65% by mass, based on the solid content of the photosensitive resin composition of the second aspect. By setting it as the said range, it is easy to acquire the balance of developability.

The acid crosslinkable substance in the photosensitive resin composition of the second aspect is not particularly limited, and a conventionally known acid crosslinkable substance can be used.

Specific examples of the acid crosslinkable substance include an amine-based resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, a guanamine resin, an acetamide resin, a benzoguanamine resin, and an acetylene urea- Formaldehyde resin, succinimide-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. These acid crosslinkable materials can be easily reacted with aldehyde by reacting melamine, urea, guanamine, acetamide, benzoguanamine, acetylene urea, amber amide, and ethylene urea in boiling water. Methylation or further alkoxylation of a lower alcohol by reaction with it. Practically, it can be obtained from a melamine resin such as NIKALAC MX-750, NIKALAC MW-30, NIKALAC MW100LM, or a urea resin such as NIKALAC MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). Further, a benzoguanamine resin such as Cymel 1123 or Cymel 1128 (manufactured by Mitsui Cyanamid Co., Ltd.) can be obtained as a commercial product.

Also, 1,3,5-glycol (methoxymethoxy)benzene can be used. a benzene compound having an alkoxy group such as 1,2,4-paraxyl (isopropoxymethoxy)benzene, 1,4-bis(sec-butoxymethoxy)benzene, 2,6-dihydroxyl A phenol compound having a hydroxyl group or an alkoxy group such as methyl-p-tert-butylphenol.

These acid crosslinkable materials may be used alone or in combination of two or more.

The content of the acid-crosslinkable material is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. When it is in the above range, the curability and patterning properties of the photosensitive resin composition are good.

The photoacid generator in the photosensitive resin composition of the second aspect is not particularly limited, and a conventionally known photoacid generator can be used.

Specific examples of the photoacid generator include a phosphonium salt generator such as a phosphonium salt or a phosphonium salt, an oxime sulfonate acid generator, a halogen-containing triazine compound, and a diazomethane acid generator. A nitrobenzyl sulfonate acid generator (nitrobenzyl derivative), a sulfonate ester acid generator, a diterpenoid generator, and the like.

The guanidine-based acid generator is preferably a compound represented by the following formula (c-1).

In the above formula (c-1), R ^c1 and R ^c2 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and R ^c3 represents that it may have a halogen atom or a p-phenylene group of an alkyl group, and R ^c4 represents a hydrogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, a benzinium group which may have a substituent, or a polyphenyl group which may have a substituent, and A ^- represents The counter ion of the cesium ion.

Specific examples of A ^- include SbF ₆ ^- , PF ₆ ^- , AsF ₆ ^- , BF ₄ ^- , SbCl ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , CH ₃ SO ₃ ^- , FSO ₃ ^- , F ₂ PO ₂ ^- , p-tosylate, nonafluorobutane sulfonate, adamantane carboxylate, tetraaryl borate, fluorinated alkyl fluorophosphate anion represented by the following formula (c-2), etc. .

[化30][(Rf) _n PF _6-n 】 ^-    (c-2)

In the above formula (c-2), Rf represents an alkyl group in which 80% or more of a hydrogen atom is substituted by a fluorine atom. n is its number and represents an integer from 1 to 5. The n Rfs may be the same or different.

The photoacid generator represented by the above formula (c-1) may, for example, be 4-(2-chloro-4-benzylindenylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate or 4-(2-chloro 4-benzylbenzylthiophenyl)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylindolylphenylthio)phenylbis(4-chloro Phenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-methylphenyl)phosphonium hexafluoroantimonate, 4-(2-chloro 4-benzylbenzylthiophenyl)phenylbis(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylsulfonylphenylthio) Phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4- (3-methyl-4-benzylindolylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-fluoro-4-benzylnonphenylthio)phenyl double (4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,6-dichloro-4 -benzylbenzylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,6-dimethyl-4-benzylsulfonylphenylthio)phenyl bis (4 -fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4 -(2-methyl-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(3-methyl-4-benzylsulfonylphenylthio) Phenyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-fluoro-4-benzylmercaptophenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4 -(2-methyl-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,3,5,6-tetramethyl-4- Benzyl phenylthio)phenyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,6-dichloro-4-benzylpyridylphenylthio)phenyl bis(4-chloro Phenyl)phosphonium hexafluoride Acid salt, 4-(2,6-dimethyl-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl 4-benzylbenzylthiophenyl)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-ethinylphenylthio)phenyldiphenylphosphonium Fluoride, 4-(2-chloro-4-(4-methylbenzyl)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-(4) -fluorobenzyl phenyl)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzyl)phenylthio)phenyldiphenyl Hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-ethenylbenzenesulfonate Phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzyl)phenylthio)phenyl bis(4-fluorophenyl)鋶 hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzyl)phenylthio)phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2) -chloro-4-(4-methoxybenzyl)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-dodecylbenzene Thio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-ethinylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimony Acid, 4-(2-chloro-4-(4-methylbenzyl)phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4) -(4-fluorobenzylidene)phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzyl) benzene Thio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluorophosphate Citrate, 4-(2-chloro-4-benzylindolylphenyl)phenyldiphenylphosphonium hexafluorophosphate, 4-(2-chloro-4-benzylindenylphenylthio)phenyl Phenylhydrazine tetrafluoroborate, 4-(2-chloro-4-benzylindolylthio)phenyldiphenylphosphonium perchlorate, 4-(2-chloro-4-benzylindenylphenylthio) )benzene Diphenylphosphonium trifluoromethanesulfonate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro- 4-benzylmercaptophenylthio)phenylbis(4-fluorophenyl)phosphonium tetrafluoroborate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)鋶Perchlorate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium trifluoromethanesulfonate, 4-(2-chloro-4- Benzyl phenyl phenyl) phenyl bis(4-fluorophenyl) 鋶p-toluene sulfonate, 4-(2-chloro-4-benzyl phenylthio) phenyl bis(4-fluorophenyl) Camphor sulfonate, 4-(2-chloro-4-benzyl phenylthio)phenyl bis(4-fluorophenyl)phosphonium hexafluorobutane Sulfonate, 4-(2-chloro-4-benzylindenylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylsulfonylbenzenesulfonate Phenyl bis(4-chlorophenyl)phosphonium tetrafluoroborate, 4-(2-chloro-4-benzylindenylphenylthio)phenylbis(4-chlorophenyl)phosphonium perchlorate, 4-(2-Chloro-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]indole Fluorinated pentafluoroethyl phosphate, diphenyl [4-(p-triphenylthio)phenyl]phosphonium hexafluoroantimonate, diphenyl [4-(p-triphenylthio)phenyl]鋶Trifluoroethylene pentafluoroethyl phosphate and the like.

Examples of the other sulfonium acid generator include a cationic moiety of the above formula (c-1), which is substituted with, for example, triphenylsulfonium, (4-tert-butoxyphenyl)diphenylphosphonium, and bis (4-). Tert-butoxyphenyl)phenylhydrazine, ginseng (4-tert-butoxyphenyl)fluorene, (3-tert-butoxyphenyl)diphenylphosphonium, bis(3-tert-butoxy Phenyl phenyl) phenyl hydrazine, ginseng (3-tert-butoxyphenyl) fluorene, (3,4-ditert-butoxyphenyl) diphenyl fluorene, bis(3,4-ditert- Butoxyphenyl)phenylhydrazine, ginseng (3,4-ditert-butoxyphenyl)anthracene, diphenyl(4-thiophenoxyphenyl)anthracene, (4-tert-butoxy Carbomethoxymethoxyphenyl)diphenylanthracene, ginseng (4-tert-butoxycarbonylmethoxyphenyl)anthracene, (4-tert-butoxyphenyl)bis(4-dimethylamine Phenyl) hydrazine, ginseng (4-dimethylaminophenyl) fluorene, 2-naphthyldiphenyl fluorene, dimethyl-2-naphthyl anthracene, 4-hydroxyphenyl dimethyl hydrazine, 4 a ruthenium cation such as methoxyphenyl dimethyl hydrazine, trimethyl hydrazine, 2-sided oxycyclohexylcyclohexylmethyl hydrazine, trinaphthyl fluorene or tribenzyl hydrazine; or diphenyl fluorene or bis (4-tert-butylphenyl)fluorene, (4-tert-butoxyphenyl)phenylhydrazine, (4-methoxyphenyl) a ruthenium cation such as an aryl sulfonium cation such as phenylhydrazine By.

The oxime sulfonate-based acid generator may, for example, be [2-(propylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene](o-methylphenyl)acetonitrile, α-( P-toluenesulfonyloxyimido)-phenylacetonitrile, α-(phenylsulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino) 1-cyclopentenylacetonitrile and the like.

Further, in addition to the above, a compound represented by the following formula (c-3) can also be mentioned.

In the above formula (c-3), R ^c5 represents a monovalent, divalent or trivalent organic group, and R ^c6 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and r represents 1~ An integer of 6.

The R ^{c5 is} particularly preferably an aromatic compound group, and examples of the aromatic compound group include an aromatic hydrocarbon group such as a phenyl group or a naphthyl group; or a heterocyclic group such as a furyl group or a thienyl group. These may also have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group or the like. Further, R ^{c6 is} particularly ^preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Further, r is preferably an integer of 1 to 3, more preferably 1 or 2.

The photoacid generator represented by the above formula (c-3), when r=1, R ^c5 is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^c6 is a Base compound. More specifically, the photoacid generator represented by the above formula (c-3) may, for example, be α-(methylsulfonyloxyimino)-1-phenylacetonitrile or α-(methylsulfonyloxy). Imino)-1-(p-methylphenyl)acetonitrile, and α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile.

The photoacid generator represented by the above formula (c-3), when r = 2, may be a photoacid generator represented by the following formula.

The halogen-containing triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-mallowyl-1,3,5-triazine or 2,4-bis(trichloromethyl)-6-[ 2-(2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl]-s -Triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethane) 6-[2-(5-propyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5- Dimethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl) Vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4 - bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6 -[2-(3-methoxy-5-propoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4- Methylenedioxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-three Pyrazine, 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-(2-bromo-4-methoxy)styrylphenyl-s-triazine 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4, 6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three Oxazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2) -furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylene Diethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, cis (1,3-dibromopropyl)-1,3,5-triazine, a halogen-containing triazine compound such as bis(2,3-dibromopropyl)-1,3,5-triazine or the like (2,3-dibromopropyl)trimeric isocyanate or the like ( C-4) A halogen-containing triazine compound.

In the above formula (c-4), R ^c7 , R ^c8 and R ^c9 each independently represent a halogenated alkyl group having 1 to 6 carbon atoms.

Further, as other photoacid generators, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl) Nitrogen methane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylphenylsulfonyl)diazomethane, Bis(3-methylphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, bis(4-fluorophenylsulfonyl)diazomethane, bis( 4-chlorophenylsulfonyl)diazomethane, bis(sulfonyl)diazomethane such as bis(4-tert-butylphenylsulfonyl)diazomethane; 2-methyl-2-(p -toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2-methanesulfonyl-2-methyl-(p-methylthio)propiophenone a sulfonylcarbonylalkane such as 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one; 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazo Methane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonate -1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-di Methyl ethylsulfonyl)-3,3-dimethyl-2-butanone, 1-ethenyl-1-(1-methylethylsulfonate Dimethylmethane, 1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone, 1-diazo-1-phenylsulfonyl-3, 3-dimethyl-2-butanone, 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, 2-diazo-2-(p-toluenesulfonate) Base) cyclohexyl acetate, 2-diazo-2-benzenesulfonyl acetic acid-tert-butyl ester, 2-diazo-2-methanesulfonyl isopropyl acetate, 2-diazo-2-benzenesulfonate Sulfhydrylcarbonyldiazomethanes such as cyclohexyl thioglycolate, 2-diazo-2-(p-toluenesulfonyl)acetic acid-tert-butyl ester; p-toluenesulfonic acid-2-nitrobenzyl a nitrobenzyl derivative such as ester, p-toluenesulfonic acid-2,6-dinitrobenzyl ester, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl ester; methane of gallicol Sulfonate, benzenesulfonate of gallicol, p-toluenesulfonate of gallophenol, p-methoxybenzenesulfonate of gallophenol, mesitylene sulfonate of gallicol, benzyl of gallicol Sulfonate, methanesulfonate of alkyl gallate, besylate of alkyl gallate, p-tosylate of alkyl gallate, alkyl of gallate P-methoxybenzenesulfonate, alkyl gallate having a carbon number of 1 to 15) A polyhydroxy compound such as a mesitylene sulfonate or a benzyl sulfonate of an alkyl gallate, and an ester of an aliphatic or aromatic sulfonic acid.

These photoacid generators can be used individually or in combination of 2 or more types.

The content of the photoacid generator is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. When it is in the above range, the curability of the photosensitive resin composition is good.

The photosensitive resin composition of the second aspect contains the compound represented by the above formula (1) as described above. The compound has good solubility in an organic solvent, and when it is contained in a photosensitive resin composition, Get good micro-patterning properties.

The content of the compound represented by the above formula (1) is preferably from 1 to 200 parts by mass, more preferably from 10 to 80 parts by mass, per 100 parts by mass of the photoacid generator. By setting it as the said range, it can obtain favorable microscopic-formation characteristics, and the favorable developability is acquired.

The photosensitive resin composition of the second aspect may further contain a compound having four or more phenolic hydroxyl groups and having a molecular weight of less than 2,000.

Specific examples of such a compound include various benzophenone compounds such as tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, and hexahydroxybenzophenone, and examples thereof include 2-hydroxy-3-(2'-hydroxy-5'-methylbenzyl)-5-methylphenyl]methane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4 -dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6 -methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, bis(4- a hydroxyaryl compound such as hydroxy-2,3,5-trimethylphenyl)-3,4-dihydroxyphenylmethane; 2-(2,3,4-trihydroxyphenyl)-2-( Bis(hydroxyphenyl) such as 2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane Alkane-based compound; poly(o-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyrene) having a molecular weight of less than 2000 , poly(α-methyl-p-hydroxystyrene), poly(4-hydroxy-3-methyl A polyhydroxystyrene compound or the like such as styrene). These benzophenone-based compounds, hydroxyaryl-based compounds, bis(hydroxyphenyl)alkane compounds, and polyhydroxystyrene-based compounds may have a substituent other than a hydroxyl group.

These compounds may be used alone or in combination of two or more.

The content of the compound having a phenolic hydroxyl group of 4 or more and having a molecular weight of less than 2,000 is preferably 0.5 to 5 parts by mass based on 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. By setting it as the said range, the phenomenon which the tip of the photosensitive resin composition is thinned can be suppressed.

The organic solvent in the photosensitive resin composition of the second aspect is exemplified as the organic solvent exemplified in the photosensitive resin composition of the first aspect.

The content of the organic solvent is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the solid content of the photosensitive resin composition of the second aspect.

The photosensitive resin composition of the second aspect may contain the above various additives as needed in the same manner as the photosensitive resin composition of the first aspect.

(3) Photosensitive resin composition of the third aspect

The photosensitive resin composition of the third aspect is a negative photosensitive film containing a photosensitive polyimide precursor, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the above formula (1), and an organic solvent. Resin composition.

The photosensitive polyimide precursor in the photosensitive resin composition of the third aspect can be, for example, a structure represented by the following formula (d-1). It is a unit and has an acid functional group and a photosensitive base in the molecule.

In the above formula (d-1), X ^d represents a tetravalent organic group which does not contain an atom having an unshared electron pair in a skeleton linking two amidino groups to which X ^d is bonded, and Y ^d represents a bond of a Y ^d bond. The two amidino group skeletons do not contain a divalent organic group having an atom having an unshared electron pair, and R ^d1 and R ^d2 each independently represent a hydroxyl group or a monovalent organic group.

In the definitions of X ^d and Y ^d , "a skeleton linking two amidoxime groups" means a skeleton formed only of atoms constituting a bonding chain connecting two indoleamine bonds. Therefore, a hydrogen atom, a fluorine atom, or the like exists as a terminal, and an atom that bonds a bond chain of two guanamine bonds is not formed, and is not included in the above-mentioned "skeleton". However, when an atom constituting a ring (an aromatic ring or an aliphatic ring) is contained in the skeleton, all of the atoms constituting the ring are contained in the above "skeleton". For example, when a benzene ring or a cyclohexyl ring is contained, the six carbon atoms constituting the benzene ring or the cyclohexyl ring itself are contained in the above "skeleton". Further, a substituent or a hydrogen atom bonded to a benzene ring or a cyclohexyl ring is not included in the "skeleton" referred to herein.

Therefore, when a carbonyl bond is present on the skeleton, the chain constituting the two guanamine groups is only a carbon atom in the carbonyl group, and therefore the oxygen atom in the carbonyl group does not constitute the above-mentioned "skeleton". Also, regarding the 2,2-propylene bond or the hexafluoro-2,2-propylene bond, only the carbon source present at the center (2 position) If the child is a skeleton, the carbon atoms (1 or 3) at both ends do not constitute the above-mentioned "skeleton". Examples of the "atom having a non-shared electron pair" include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. On the other hand, "an atom having no unshared electron pair" may, for example, be a carbon atom or a germanium atom.

The photosensitive polyimide precursor, X ^d is not contained in the framework if those atoms having an unshared electron pair to the like as described above, is, when swollen due to the less alkaline development, it is preferred. For the same reason, Y ^{d is} preferably not contained in an atom whose skeleton has an unshared electron pair.

Further, in the photosensitive polyimide precursor, if it has a Y ^d2 containing a ruthenium atom, for example, a siloxane-containing bond, as a part thereof, instead of Y ^d in the constituent unit, it can be imparted. It is preferable because of high substrate adhesion. In this case, the ratio is preferably from 1 to 20 mol% of the total diamine residue of the photosensitive polyimide precursor.

The X ^d and Y ^d in the above formula (d-1) are preferably an alkyl group having 4 to 20 carbon atoms or a cycloalkyl group; or an aromatic ring having a carbon number of 6 to 20 such as a benzene ring or a naphthalene ring; 2 to 10 of these aromatic rings are bonded by a single bond, an alkyl group, a fluorinated alkyl group, a carbonyl group or the like. Further, these may have a substituent such as a hydrocarbon group, a halogenated hydrocarbon group or a halogen atom on the aromatic ring. Further, among these X ^d and Y ^d , the atoms directly bonded to the atoms constituting the skeleton are also "atoms having no unshared electron pair", and are preferable because of their high effects. Further, in this definition, as in the case of a carbonyl group, those which directly bond oxygen atoms on a carbon atom constituting the skeleton or a fluorine atom bonded to a carbon atom constituting the skeleton are contained. Further, X ^d and Y ^{d are} preferably those having no fluorine atom.

The acidity of the molecule of the photosensitive polyimide precursor The functional group may, for example, be a carboxyl group, a phenolic hydroxyl group or a sulfonic acid group, and among them, a carboxyl group is preferred. Further, as the photosensitive group, a vinyl group, an allyl group, an acrylonitrile group, a methacryl fluorenyl group, an acryloxy group, a methacryloxy group, or the like containing an ethylenically unsaturated bond is preferable. It is an acrylonitrile group, a methacryloyl group, an acryloxy group, and a methacryloxy group.

In the photosensitive polyimine precursor, the acid functional group is preferably such that R ^d1 or R ^d1 in the constituent unit of the above formula (d-1) is present as a hydroxyl group (that is, a carboxyl group is formed), or Y ^{d is} present in the diamine residue. Further, the photosensitive group is preferably a side chain represented by R ^d1 or R ^d2 in the above formula (d-1) or a diamine residue represented by Y ^d , for example, as a bond to an aromatic ring. The base of the aromatic ring of the amine residue is present.

^{Among the} R ^d1 and R ^d2 , a monovalent organic group having a photosensitive group is represented by the following formula.

In the above formula, R ^d3 and R ^d4 each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ^d5 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ^d6 represents a hydrogen atom or a methyl group.

Further, among R ^d1 and R ^d2 , a monovalent organic group having no photosensitive group may, for example, be an alkoxy group having 1 to 15 carbon atoms or an alkylamine group.

The photosensitive polyimide precursor is preferably 50 to 100 mol% of the constituent unit represented by the above formula (d-1); more preferably, it has only the constituent unit represented by the above formula (d-1). Or the structural unit represented by the above formula (d-1) and the Y ^d in the above formula (d-1) are constituent units of a divalent organic group containing a ruthenium atom.

The photosensitive polyimide precursor can be obtained by using a tetracarboxylic dianhydride, a diamine, and a compound having a photosensitive group as a material, and various known production methods can be applied.

As the tetracarboxylic dianhydride, to impart X ^d are concerned, examples thereof include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 1,2,5,6 -naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-nonanedicarboxylic acid Dihydride, m-terphenyl--3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 4,4 '- Hexafluoroisopropylidene diphthalic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

As the diamine, for the case of imparting Y ^d , preferred examples thereof include 2,2'-dimethyl-4,4'-diaminobiphenyl and 3,3'-dimethyl-4,4. '-Diaminobiphenyl, 2,2',6,6'-tetramethyl-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4 '-Diaminobiphenyl, 4,4'-(or 3,4-,3,3'-, 2,4-, 2,2'-)diaminodiphenylmethane, p-xylene Amine, m-xylenediamine, 4,4'-methylene-bis-(2,6-diethylaniline), 4,4'-methylene-bis-(2,6-diisopropyl Aniline), 1,5,-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2'-hexafluorodimethyl-4,4'-diaminobiphenyl, 3,3'-hexafluorodimethyl-4,4'-diaminobiphenyl, 4,4'-hexafluoroisopropylidene diphenylamine, 1,1,1,3,3,3-hexafluoro -2,2-bis(4-aminophenyl)propane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-benzene Amine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4,6-trimethyl-1,3-phenylenediamine, 2,7-diaminopurine, 4,4 -diamino octafluorobiphenyl, 2,2-hexafluorodimethyl-4,4'-diaminobiphenyl, etc., such diamines, Alone or in combination of two or more thereof.

Further, Y ^d may be at least one phenolic hydroxyl group or carboxyl group as an acid functional group if it is a difunctional amine which does not include an atom having an unshared electron pair on the skeleton of the linking amine group. Preferred examples thereof include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, and bis ( 4-amino-3-carboxyphenyl)methylene, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxyl -2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-4,4 '-Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-amino- 3-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-carboxyphenyl)methane, 4,4'-diamino-2,2'-dicarboxybiphenyl, and the like. These are used alone or in combination of two or more kinds together with the diamine.

Further, as the Y ^2d which contains a ruthenium atom, an aliphatic diamine such as a diaminopolysiloxane represented by the following formula (d-2) can be mentioned.

In the above formula (d-2), s, t, and u each independently represent an integer of 1 to 10.

When the aliphatic diamine is used, the blending amount is preferably 20 mol% or less of all the diamines from the viewpoint of less swelling during development and heat resistance of the formed film.

The polyimine precursor to be a photosensitive group may, for example, be a compound which has a group having an ethylenically unsaturated bond and an amine group or a 4-staged salt thereof, and a carboxyl group and an amine group of the polyglycolic acid or A method in which a portion of a 4-stage salt is subjected to an ion-bonded polyimine precursor; a method in which an ethylenic unsaturated bond is introduced into a side chain by a covalent bond such as an ester bond or a guanamine bond;

Among these, in particular, a photosensitive polyimide intermediate (polyglycolate) in the form of an ethylenically unsaturated bond introduced by an ester bond is suitable for alkali development. When an ethylenically unsaturated bond is introduced by an ester bond, the amount of the compound having an ethylenically unsaturated bond is based on the reactivity of the alkali, solubility, hardenability, heat resistance, and the like, and is based on the polyamine. The total amount of the carboxyl group is preferably from 85 to 25 mol%, and the remainder is maintained as a carboxyl group (i.e., a polyamido acid partial ester).

Examples of the compound in which an ethylenically unsaturated bond is introduced by an ester bond include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and acrylic acid. 4-hydroxybutyl ester, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2-(methacryloxyloxy) Ethyl ester, dicaprolactone 2-(methacryloxy)ethyl ester, caprolactone 2-(propylene decyloxy) ethyl ester, dicaprolactone 2-(propylene decyloxy) ethyl ester, and the like.

The mass average molecular weight of the photosensitive polyimide precursor is preferably from 5,000 to 80,000.

The content of the photosensitive polyimide precursor is preferably from 40 to 95% by mass, more preferably from 55 to 90% by mass, based on the solid content of the photosensitive resin composition of the third aspect. By setting it as the said range, it is easy to acquire the balance of developability.

The photopolymerizable monomer in the photosensitive resin composition of the third aspect is exemplified as the photopolymerizable monomer exemplified in the photosensitive resin composition of the first aspect.

The content of the photopolymerizable monomer is preferably 5 to 100 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the photosensitive polyimide precursor. When it is in the above range, it tends to easily obtain a balance between sensitivity, developability, and resolution.

The photopolymerization initiator of the photosensitive resin composition of the third aspect is exemplified by the photopolymerizable initiator which is exemplified in the photosensitive resin composition of the first aspect.

The content of the photopolymerization initiator is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the photosensitive polyimide precursor. When it is in the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved and the curing failure can be suppressed.

The photosensitive resin composition of the third aspect contains the compound represented by the above formula (1) as described above. The compound is soluble in organic matter The solubility of the agent is good, and when it is contained in the photosensitive resin composition, good patterning properties can be obtained.

The content of the compound represented by the above formula (1) is preferably from 0.5 to 50% by mass, more preferably from 1 to 20% by mass, based on the solid content. By setting it as the said range, it can obtain favorable microscopic-formation characteristics, and the favorable developability is acquired.

The organic solvent in the photosensitive resin composition of the third aspect is exemplified as the organic solvent exemplified in the photosensitive resin composition of the first aspect. Among them, a polar solvent in which the produced polyimine is completely dissolved is particularly preferable. Examples of such a polar solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, and tetramethyl urea. , trimethylamine hexamethyl phosphate, γ-butyrolactone, and the like.

The content of the organic solvent is preferably such that the solid content concentration of the photosensitive resin composition of the third aspect is from 1 to 50% by mass, more preferably from 5 to 30% by mass.

The photosensitive resin composition of the third aspect may contain the above various additives as needed, similarly to the photosensitive resin composition of the first aspect.

(4) Photosensitive resin composition of the fourth aspect

The photosensitive resin composition of the fourth aspect contains a polyimide precursor, a compound represented by the above formula (1), and an organic solvent. It is preferred to further contain a sensitizer.

Polyimine in the photosensitive resin composition of the fourth aspect As the precursor, for example, polylysine having a constituent unit represented by the following formula (e-1) can be used.

In the above formula (e-1), R ^e1 represents a tetravalent organic group, R ^e2 represents a divalent organic group, and R ^e3 and R ^e4 represent a hydrogen atom or a monovalent organic group.

When R ^e3 and R ^e4 are a monovalent organic group, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a structure represented by C _x H _2x OC _y H _2y+1 containing an ether bond therein may, for example, be mentioned. Wait.

As the polyimine precursor, from the viewpoint of alkali developability, a polyamic acid such as R ^e3 and R ^e4 as a hydrogen atom is suitably used.

Further, the tetravalent value of R ^e1 represents only the valence for bonding with an acid, and may further have a substituent. Similarly, the valence of R ^e2 represents only the valence for bonding with an amine, and may further have a substituent.

Polylysine is obtained by a reaction of an acid dianhydride and a diamine, and is excellent in heat resistance and dimensional stability of the finally obtained polyimine. In the above formula (e-1), it is preferred. R ^e1 or R ^e2 is an aromatic group, and more preferably R ^e1 and R ^e2 are aromatic groups. In this case, in R ^e1 of the above formula (e-1), the four groups ((-CO-) ₂ (-COOH) ₂ ) to which the R ^e1 is bonded may be bonded to the same aromatic ring or may be bonded. In different aromatic rings. Similarly, in R ^e2 of the above formula (e-1), the two groups ((-NH-) ₂ ) to which R ^e2 is bonded may be bonded to the same aromatic ring or may be bonded to different aromatic rings.

The polylysine represented by the above formula (e-1) may be composed of a single constituent unit or may be composed of two or more repeating units.

A method of producing a polyimide precursor can be applied to a conventionally known method. For example, (1) a method of synthesizing a precursor of a prodrug from an acid dianhydride and a diamine, and (2) reacting an acid dianhydride with a monohydric alcohol, an amine compound, an epoxy compound, etc., and then The method of synthesizing a polycarbimine precursor by reacting a carboxylic acid of a synthesized ester acid or a amic acid monomer with a diamine compound or a derivative thereof is not limited thereto.

The acid dianhydride which can be applied to the reaction for obtaining a polyimide precursor is exemplified by ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutene. An aliphatic tetracarboxylic dianhydride such as an alkyltetracarboxylic dianhydride or a cyclopentane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid Anhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4 '-Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2' 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane II Anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane Anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1, 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-double [(3,4-Dicarboxy)benzylidene]phthalic anhydride, 1,4-bis[(3,4-dicarboxy)benzylidene]phthalic anhydride, 2,2-bis{4-[4- (1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, double {4-[4-(1,2-Dicarboxy)phenoxy]phenyl}one dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}one dianhydride 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3-(1,2-dicarboxy)phenoxy]biphenyl Diacetate, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}one dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl } Keto dianhydride, bis {4-[4-(1,2-dicarboxy)phenoxy]phenyl}phosphinic anhydride, bis{4-[3-(1,2-dicarboxy)phenoxy] Phenyl}ruthenic anhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}thioether dianhydride, bis{4-[3-(1,2-dicarboxy)benzene Oxy]phenyl}thioether dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3, 3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,3,6,7-decanetetracarboxylic acid Acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinium tetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m-triphenyl-3,3',4,4 An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride or p-terphenyl-7,3',4,4'-tetracarboxylic dianhydride.

These acid dianhydrides can be used individually or in combination of 2 or more types.

Can be applied to obtain the reaction of the polyimide precursor Examples of the diamine include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether. 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diamino group Phenyl sulfide, 3,3'-diaminodiphenyl fluorene, 3,4'-diaminodiphenyl fluorene, 4,4'-diaminodiphenyl fluorene, 3,3'-di Aminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4' -diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl) Propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3 -hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4 -aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-di ( 4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, 1,3-double ( 3-aminophenoxy)benzene, 1,3- (4-Aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-double (3 -aminobenzylbenzyl)benzene, 1,3-bis(4-aminobenzylbenzyl)benzene, 1,4-bis(3-aminobenzylbenzyl)benzene, 1,4-bis(4-amine Benzylidene)benzene, 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl Benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene, 1 , 3-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-di-trifluoromethylbenzyl)benzene , 1,4-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-di-trifluoromethylbenzyl Benzene, 2,6-bis(3-aminobenzene) Oxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-amine Phenyloxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl]one, bis[4-(3 -aminophenoxy)phenyl]thioether, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]anthracene, Bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)benzene Ether, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) Phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,3-double [4-(4-Aminophenoxy)benzylidene]benzene, 1,4-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,4-bis[4-( 4-aminophenoxy)benzylidene]benzene, 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-double [ 4-(4-Aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl Benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4'-bis[4-(4-aminophenoxy) Benzyl hydrazide]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-double [4-(4-Amino-α,α-dimethylbenzyl)phenoxy]diphenylanthracene, 4,4'-bis[4-(4-aminophenoxy)phenoxy] Diphenylanthracene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybiphenyl Ketone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3- Aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirodioxane, 6,6'-bis(4-amine Aromatic amines such as phenoxy)-3,3,3',3'-tetramethyl-1,1'-spirodecane; 1,3-bis(3-aminopropyl)tetramethyl Dioxazane, 1,3-bis(4-aminobutyl)tetramethyldioxane, α,ω-bis(3-aminopropyl)polydimethyloxane, α, Ω-bis(3-aminobutyl)polydimethyloxane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, Bis(2-aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxylate Ethyl, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis (3) -aminopropyl)ether, triethylene glycol bis(3-aminopropyl)ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10- An aliphatic amine such as diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane; 1,2-diamino ring Alkane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(2-aminoethyl)cyclohexane, 1,3-bis(2-amine Ethyl ethyl) cyclohexane, 1,4-bis(2-aminoethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 2,6-bis(aminomethyl)bicyclo[2.2 .1] an alicyclic diamine such as heptane or 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane. Further, a part or all of the hydrogen atom on the aromatic ring of the above diamine may be substituted with a substituent selected from the group consisting of a fluorine group, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. Diamine.

These diamines can be used individually or in combination of 2 or more types.

The content of the polyimine precursor is preferably from 50 to 99% by mass, more preferably from 70 to 95% by mass, based on the solid content of the photosensitive resin composition of the fourth aspect. By setting it as the said range, the coating film formation capability can be improved.

The photosensitive resin composition of the fourth aspect contains the compound represented by the above formula (1) as described above. This compound has good solubility in an organic solvent, and when it is contained in a photosensitive resin composition, good micro patterning property can be obtained.

The content of the compound represented by the above formula (1) is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the polyimide precursor. By setting it as the said range, it can obtain favorable microscopic-formation characteristics, and the favorable developability is acquired.

The organic solvent in the photosensitive resin composition of the fourth aspect is exemplified as the organic solvent exemplified in the photosensitive resin composition of the first aspect. Among them, propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N- A polar solvent such as methyl-2-pyrrolidone or γ-butyrolactone or an aromatic hydrocarbon such as toluene or the like and a mixed solvent thereof are preferred.

The content of the organic solvent is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the solid content of the photosensitive resin composition of the fourth aspect.

When the photosensitive resin composition of the fourth aspect is a positive photosensitive resin composition, it is preferred to further contain a photoacid generator as a photosensitizer. The photoacid generator can be exemplified in the photosensitive resin composition of the second aspect. Examples of the above include a compound containing a quinonediazide group. The compound containing a quinonediazide group may, for example, be an ortho-quinonediazide compound or a diazonaphthoquinone compound, and for example, a phenol compound (also referred to as a compound having a phenolic hydroxyl group) and a naphthoquinonediazidesulfonic acid compound are preferable. a fully esterified or partially esterified compound; an ortho-quinonediazide compound obtained by subjecting o-quinonediazidesulfonyl chloride to a condensation reaction with a hydroxy compound or an amine compound in the presence of a dehydrochlorinating agent (of which From 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, with 1-naphthoquinone-2 An ester compound obtained by the reaction of -azide-5-sulfonyl chloride is preferred).

Others may contain a thermal crosslinking agent, a cerium-containing compound, a non-polymerizable binder polymer, a solvent, an elastomer, a dissolution promoter, a dissolution inhibitor, a surfactant or a leveling agent, a thermal acid generator, etc., as needed. Other ingredients.

The thermal crosslinking agent is not particularly limited as long as it is a compound which is crosslinked or polymerized in the step of heat treatment after development, and preferably has a methylol group, an alkoxymethyl group, or an epoxy group in the molecule. A compound based on a vinyl ether group. For example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6 - pyridine dimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylenebis(2,6-dialkoxymethylphenol), etc. having a hydroxymethyl group a compound; 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4' - bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, methyl 2,6-naphthalene dicarboxylate, 4,4'-methylene double (2 , 6-dimethoxymethylphenol), etc. a compound; a methylol melamine compound such as hexamethylol melamine or hexabutanol melamine; an alkoxy melamine compound such as hexamethoxy melamine; or an alkoxymethyl acetylene such as tetramethoxymethyl acetylene urea; a urethane compound, a methylol benzoguanamine compound, a hydroxymethyl urea compound such as dimethylol ethylene urea; a cyano compound derived from dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid or the like; , isocyanate compound such as 4-phenylene diisocyanate or 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, three Polyglycidyl polyisocyanate, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, phenol novolac resin epoxy resin, etc. a compound of an epoxy group; a maleic imine compound such as N,N'-1,3-benzene dimaleimide, N,N'-methylene dimaleimide, etc., but not Limited to this. These thermal crosslinking agents may be used alone or in combination of two or more.

The ruthenium-containing compound may, for example, be an anthracene-containing resin, a ruthenium-containing resin precursor, a decane coupling agent or the like, preferably a decane coupling agent; more preferably 1-(2-pyridyl)-3-[3-(trimethoxydecane) A ureido-containing decane coupling agent such as propyl]urea or 1-(3-pyridyl)-3-[3-(triethoxydecyl)propyl]urea.

When the photosensitive resin composition of the fourth aspect is a negative photosensitive resin composition, it is preferred to further contain a photobase generator as a photosensitizer. The photobase generator is not particularly limited, and may be suitably the same as the above-described oxime ester compound in the photosensitive resin composition of the first aspect.

Negative photosensitive resin composition, other can be included as needed There are other components similar to those of the above positive photosensitive resin composition.

In the photosensitive resin composition of the fourth aspect, the ratio of each component other than the compound represented by the above formula (1) is as follows.

The content of the polyimine precursor is preferably 50% by mass or more, and more preferably 60 to 90% by mass based on the total solid content of the photosensitive composition.

The content of the sensitizer is preferably from 3 to 50 parts by mass, more preferably from 5 to 30 parts by mass, per 100 parts by mass of the polyimine precursor, from the viewpoint of sensitivity and the like.

The content of the thermal crosslinking agent is preferably from 1 to 50 parts by mass based on 100 parts by mass of the polyimide precursor.

The content of the decane compound is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the polyimide precursor.

The solid content concentration of the photosensitive resin composition is preferably 30% by mass or less, more preferably 1 to 20% by mass, still more preferably 5 to 15% by mass.

The photosensitive resin composition of the fourth aspect may contain the above various additives as needed in the same manner as the photosensitive resin composition of the first aspect.

(5) photosensitive resin composition of the fifth aspect

The photosensitive resin composition of the fifth aspect contains an epoxy resin, a compound represented by the above formula (1), and an organic solvent.

The epoxy resin in the photosensitive resin composition of the fifth aspect may, for example, be a bisphenol A type ring derived from bisphenol A and epichlorohydrin. Oxygen resin, bisphenol F type epoxy resin derived from bisphenol F and epichlorohydrin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A Novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type Polyfunctional epoxy resin such as epoxy resin, fluorene epoxy resin, trifunctional epoxy resin or tetrafunctional epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, B A uret urea type epoxy resin, a trimeric isocyanate type epoxy resin, an aliphatic chain epoxy resin, or the like. These epoxy resins can be halogenated or hydrogenated.

Commercially available epoxy resin products include, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resins Co., Ltd., and Epiclon 830 manufactured by DIC Corporation. EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., Celloxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel, Epolead series, EHPE series, Nippon Steel Chemical Co., Ltd. YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxy polyether synthesized from bisphenols and epichlorohydrin, having epoxy groups at both ends; YP series, etc.), NagaseChemteX The Denacol series manufactured by the company and the Epolight series manufactured by Kyoeisha Chemical Co., Ltd. are not limited thereto.

These epoxy resins may be used alone or in combination of two or more.

The content of epoxy resin, relative to the sensitivity of the fifth aspect The solid content of the resin composition is preferably 55 to 99% by mass, more preferably 70 to 95% by mass. By setting it as the said range, the coating film formation capability can be improved.

The photosensitive resin composition of the fifth aspect contains the compound represented by the above formula (1) as described above. The compound has good solubility in an organic solvent, and when it is contained in a photosensitive resin composition, good micro patterning properties can be obtained.

The content of the compound represented by the above formula (5) is preferably from 1 to 30 parts by mass based on 100 parts by mass of the epoxy resin. By setting it as the said range, it can obtain favorable microscopic-formation characteristics, and the favorable developability is acquired.

The organic solvent in the photosensitive resin composition of the fifth aspect is exemplified as the organic solvent exemplified in the photosensitive resin composition of the first aspect. Among them, propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-A A polar solvent such as a thiopyridinone or a γ-butyrolactone or an aromatic hydrocarbon such as toluene or the like and a mixed solvent thereof are preferred.

The content of the organic solvent is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the solid content of the photosensitive resin composition of the fifth aspect.

The photosensitive resin composition of the fifth aspect may contain the above various additives as needed in the same manner as the photosensitive resin composition of the first aspect.

Further, the epoxy group-containing polycarboxylic acid in the sixth aspect described later The resin does not limit the total epoxy group to be consumed by the reaction with the "monocarboxylic acid having an alcoholic hydroxyl group" and the "polybasic acid anhydride". Usually, the resin has a residual epoxy group and is equivalent to the fifth. An epoxy resin in a photosensitive resin composition. In this case, as the epoxy resin in the photosensitive resin composition of the fifth aspect, the epoxy group-containing polycarboxylic acid resin in the photosensitive resin composition of the sixth aspect may be used. In the present invention, among the epoxy resins in the photosensitive resin composition of the fifth aspect, the epoxy group-containing polycarboxylic acid resin in the photosensitive resin composition of the sixth aspect is referred to as Non-carboxylic acid modified epoxy resin.

(6) The photosensitive resin composition of the sixth aspect

The photosensitive resin composition of the sixth aspect is a negative photosensitive resin composition containing an epoxy group-containing polycarboxylic acid resin, a photoacid generator, a compound represented by the above formula (1), and an organic solvent.

In the epoxy group-containing polycarboxylic acid resin in the photosensitive resin composition of the sixth aspect, for example, an epoxy compound having two or more epoxy groups in one molecule and one or more molecules in one molecule can be used. The monocarboxylic acid of the alcoholic hydroxyl group is reacted, and the obtained reactant is further reacted with a polybasic acid anhydride.

Examples of the epoxy compound having two or more epoxy groups in one molecule include a novolak type epoxy resin, a bisphenol type epoxy resin, a trisphenol methane type epoxy resin, and a bis(2,3-epoxy group). Propyl)trimeric isocyanate, biphenyl diglycidyl ether, alicyclic epoxy resin, copolymerized epoxy resin, and the like.

Examples of the novolak-type epoxy resin include a novolak obtained by reacting a phenol such as phenol, cresol, a halogenated phenol or an alkylphenol with formaldehyde under an acidic catalyst, and an epichlorohydrin or a methyl group. The chlorohydrin reaction is obtained. Commercially available products include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1027, EPPN-201, and BREN-S (all manufactured by Nippon Kayaku Co., Ltd.); DEN-431 and DEN-439 (both Dow) N-730, N-770, N-865, N-665, N-673, VH-4150 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and the like.

Examples of the bisphenol type epoxy resin include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin or methyl epichlorohydrin, or The bisphenol A or bisphenol F diglycidyl ether and the bisphenol condensate are reacted with epichlorohydrin or methyl epichlorohydrin to obtain the same. Commercially available products include Epikote 1004, Epikote 1002, Epikote 4002, and Epikote 4004 (all manufactured by Yuka Shell Epoxy Co., Ltd.).

Examples of the trisphenol methane type epoxy resin include those obtained by reacting trisphenol methane or tricresol methane with epichlorohydrin or methyl epichlorohydrin. Commercially available products include EPPN-501 and EPPN-502 (both manufactured by Nippon Kayaku Co., Ltd.).

Examples of the alicyclic epoxy resin include Celloxide 2021 manufactured by Daicel Chemical Industry Co., Ltd.; Epomic VG-3101 manufactured by Mitsui Petrochemical Co., Ltd.; E-1031S manufactured by Yuka Shell Epoxy Co., Ltd., EPB-13, EPB manufactured by Japan Soda Co., Ltd. -27 and so on. Further, examples of the copolymerized epoxy resin include glycidyl methacrylate, styrene, and α-methyl group. A copolymer of styrene, CP-50M, CP-50S, manufactured by Nippon Oil & Fats Co., Ltd.; or a copolymer of glycidyl methacrylate, cyclohexylmaleimide or the like.

Among the epoxy resins having two or more epoxy groups in one molecule, for example, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, a bisphenol type epoxy resin, or the like may be mentioned. A trisphenol methane type epoxy resin or the like. Particularly preferred is a polycondensate of α-hydroxyphenyl-ω-hydrogen (biphenyldimethylene-hydroxyphenyl) and 1-chloro-2,3-epoxypropane, and α-2, 3-Epoxypropoxyphenyl-ω-hydropoly{2-(2,3-epoxypropoxy)-benzylidene-2,3-epoxypropoxyphenylene}.

Examples of the monocarboxylic acid having one or more alcoholic hydroxyl groups in one molecule include, for example, dimethylolpropionic acid, dimethylol acetic acid, dimethylolbutanoic acid, dimethylol oxalic acid, and dimethylol. A hydroxymonocarboxylic acid such as hexanoic acid or hydroxytrimethylacetic acid. Among these, a monocarboxylic acid having 1 to 5 alcoholic hydroxyl groups in one molecule is particularly preferred.

Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, and benzene. Tricarboxylic anhydride, pyromellitic anhydride, and the like.

The reaction of the above epoxy compound with the above monocarboxylic acid is preferably from 0.1 to 0.7 mol, more preferably from 0.2 to 0.5 mol, based on 1 equivalent of the epoxy group of the epoxy compound. In this reaction, it is preferred to use an organic solvent which does not react with an epoxy compound or a polybasic acid anhydride and which does not have a hydroxyl group or a carboxyl group. Further, in order to promote the reaction, a catalyst can be used (for example Triphenylphosphine, benzyldimethylamine, trialkylammonium chloride, triphenylphosphonium halide, etc.). When a catalyst is used, it is preferable that the catalyst is inactivated by using an organic peroxide or the like after completion of the reaction, and it is preferable because it is stable and has good storage stability. The amount of the reaction catalyst used is preferably from 0.1 to 10% by weight based on the reaction mixture, and the reaction temperature is preferably from 60 to 150 °C. Thereby, a reaction product of the above epoxy compound and the above monocarboxylic acid can be obtained.

In the reaction of the reactant with the polybasic acid anhydride, it is preferred to react a polybasic acid anhydride having an acid value of the epoxy group-containing polycarboxylic acid resin finally obtained in an amount of 50 to 150 mgKOH/g. The reaction temperature is preferably from 60 to 150 °C. Thus, an epoxy group-containing polycarboxylic acid resin can be obtained.

These epoxy group-containing polycarboxylic acid resins may be used alone or in combination of two or more.

The content of the epoxy group-containing polycarboxylic acid resin is preferably from 30 to 80% by mass, and more preferably from 40 to 70% by mass, based on the solid content of the photosensitive resin composition of the sixth aspect. By setting it as the said range, the coating film formation capability can be improved.

The photoacid generator in the photosensitive resin composition of the sixth aspect is exemplified by the photoacid generator exemplified in the photosensitive resin composition of the second aspect.

The content of the photoacid generator is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, based on the solid content of the photosensitive resin composition of the sixth aspect. When it is in the above range, the curability of the photosensitive resin composition is good.

The photosensitive resin composition of the sixth aspect, as described above, It contains the compound represented by the above formula (1). The compound has good solubility in an organic solvent, and when it is contained in a photosensitive resin composition, good micro patterning properties can be obtained.

The content of the compound represented by the above formula (1) is preferably from 1 to 500 parts by mass, more preferably from 50 to 300 parts by mass, per 100 parts by mass of the photoacid generator. By setting it as the said range, it can obtain favorable microscopic-formation characteristics, and the favorable developability is acquired.

The photosensitive resin composition of the sixth aspect may further contain a sensitizer. As the sensitizer, for example, a ruthenium compound having an alkoxy group at the 9-position and the 10-position (9,10-dialkoxy-anthracene derivative) is preferable. The alkoxy group may, for example, be an alkoxy group having 1 to 4 carbon atoms. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having a sulfonic acid group, and an alkyl carboxylate group. The alkyl group in the alkyl sulfonate group or the alkyl carboxylate group may, for example, be an alkyl group having 1 to 4 carbon atoms. The substitution position of these substituents is preferably 2 positions.

The 9,10-dialkoxy-indole derivative may, for example, be 9,10-dimethoxy-hydrazine, 9,10-diethoxy-fluorene, 9,10-dipropoxy-fluorene, 9 , 10-dimethoxy-2-ethyl-indole, 9,10-diethoxy-2-ethyl-indole, 9,10-dipropoxy-2-ethyl-indole, 9,10 -Dimethoxy-2-chloro-indole, methyl 9,10-dimethoxyindole-2-sulfonate, methyl 9,10-diethoxyindole-2-sulfonate, 9,10- Methyl dimethoxy hydrazine-2-carboxylate, and the like.

These compounds can be treated as a 9,10-dihydroxyindole by treating the anthracene derivative in an aqueous alkali solution with a reducing agent such as zinc dust, bisulfite, palladium-carbon or sodium borohydride. Sulfuric acid Sulfate such as methyl ester or diethyl sulfate; tosylate of methyl tosylate, ethyl toluenesulfonate, propyl tosylate, monoethylene glycol tosylate; or toluenesulfonic acid A benzenesulfonate such as an ester, ethyl benzenesulfonate or propyl benzenesulfonate is obtained by alkoxylating the 9,10 position.

These sensitizers can be used individually or in combination of 2 or more types.

The content of the sensitizer is preferably from 0.1 to 6, more preferably from 0.2 to 4, based on the molar ratio of the photoacid generator. When it is in the above range, the sensitivity and the curability of the photosensitive resin composition are good.

The photosensitive resin composition of the sixth aspect may further contain a modified component for adjusting moisture resistance, heat resistance, adhesion, and the like. The modified component may be one which is cured by heat or ultraviolet rays, or may be reacted with a residual hydroxyl group or carboxyl group of the epoxy group-containing polycarboxylic acid resin by heat or ultraviolet rays. Specifically, an epoxy compound having one or more epoxy groups in one molecule, a melamine derivative (for example, hexamethoxy melamine, hexaoxylated melamine, condensed hexamethoxy melamine, etc.), bisphenol A may be mentioned. A compound (for example, tetramethylol bisphenol A or the like), an oxazoline compound or the like.

Examples of the epoxy compound having one or more epoxy groups in one molecule include Epikote 1009 and 1031 (all manufactured by Yuka Shell Co., Ltd.), Epiclon N-3050, and N-7050 (all manufactured by Dainippon Ink and Chemicals, Inc.). , DER-642U, DER-673MF (all manufactured by Dow Chemical Co., Ltd.), etc., bisphenol A type epoxy resin; ST-2004, ST-2007 (all manufactured by Dongdu Chemical Co., Ltd.), etc. Hydrogenated bisphenol A type ring Oxygen resin; YDF- 2004, YDF-2007 (all manufactured by Dongdu Chemical Co., Ltd.) and other bisphenol F-type epoxy resins; SR-BBS, SR-TBA-400 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.), YDB-600, YDB-715 ( All of them are brominated bisphenol A type epoxy resins such as those manufactured by Dongdu Chemical Co., Ltd.; and novolak type epoxy resins such as EPPN-201, EOCN-103, EOCN-1020, and BREN (all manufactured by Nippon Kayaku Co., Ltd.); A phenolic varnish type epoxy resin of bisphenol A such as Epiclon N-880 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Epiclon TSR-601 manufactured by Dainippon Ink Chemical Industry Co., Ltd. or rubber of R-1415-1 manufactured by ACR Co., Ltd. Modified epoxy resin; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., or bisphenol S-type epoxy resin such as Epiclon EXA-1514 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Blemmer DGT manufactured by Nippon Oil & Fats Co., Ltd. Diglycidyl carboxylic acid ester; trimeric isocyanuric acid triglycidyl ester of TEPIC manufactured by Nissan Chemical Co., Ltd.; bisxylenol type epoxy resin such as YX-4000 manufactured by Yuka Shell Co., Ltd.; YL- by Yuka Shell Co., Ltd. A bisphenol type epoxy resin such as 6056; an alicyclic epoxy resin such as Celloxide 2021 manufactured by Daicel Chemical Industry Co., Ltd., or the like.

The content of the modified component is preferably 50% by mass or less, and more preferably 30% by mass or less based on the solid content of the photosensitive resin composition of the sixth aspect.

The photosensitive resin composition of the sixth aspect may further contain barium sulfate, barium titanate, cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, or aluminum oxide in order to further improve characteristics such as adhesion and hardness. A well-known filler such as mica.

The content of the filler, relative to the photosensitive resin composition of the sixth aspect The solid content is preferably 60% by mass or less, more preferably 5 to 40% by mass.

The photosensitive resin composition of the sixth aspect may further contain a coloring agent such as phthalocyanine blue, phthalocyanine green, disazo yellow, crystal violet, titanium oxide or carbon black; ultrafine powder of cerium oxide and montmorillonite; A tackifier such as earth; an antifoaming agent such as a polyfluorene-based polymer or a fluorine-based polymer; and/or a leveling agent; and an additive such as an adhesion-promoting agent such as a decane coupling agent.

The organic solvent in the photosensitive resin composition of the sixth aspect is exemplified as the organic solvent exemplified in the photosensitive resin composition of the first aspect.

The content of the organic solvent is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the solid content of the photosensitive resin composition of the sixth aspect.

The photosensitive resin composition of the sixth aspect may contain the above various additives as needed in the same manner as the photosensitive resin composition of the first aspect.

<Method of Preparing Photosensitive Resin Composition>

The photosensitive resin composition of the present invention is prepared by mixing the above components with a stirrer. Further, it is also possible to filter by using a membrane filter or the like to make the prepared photosensitive resin composition uniform.

Pattern Formation Method

The pattern forming method of the present invention uses the photosensitive resin of the present invention. The composition forms a coating film or a molded body, and the coating film or the molded body is irradiated with electromagnetic waves in a specific pattern and developed.

More specifically, first, a coating film or a molded body is formed by a suitable coating method or molding method. For example, a non-contact type such as a contact transfer type coating device, a rotator (rotary coating device), a curtain coater, or the like can be used by using a roll coater, a reverse coater, a bar coater or the like. In the coating device, a photosensitive resin composition is applied onto a substrate and dried to form a coating film. The drying method is not particularly limited, and examples thereof include (1) prebaking at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, and (2) placing at room temperature. A method of several hours to several days, (3) a method of removing a solvent by placing a tens of minutes to several hours in a warm air heater or an infrared heater.

Next, the coating film or the molded body is irradiated with electromagnetic waves in a specific pattern and exposed. The electromagnetic wave may be irradiated through a positive or negative mask or may be directly irradiated. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 5 to 500 mJ/cm ² .

Next, the exposed coating film or the formed body is developed with a developing solution to form a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developer include organic compounds such as monoethanolamine, diethanolamine, and triethanolamine; or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt.

For the pattern after development, it is preferred to perform post-baking at about 200 to 250 °C.

"Cured film, insulating film, color filter, display device"

The cured film, the insulating film, and the color filter of the present invention are formed by using the photosensitive resin composition of the present invention.

For example, a coating film is formed by using a photosensitive resin composition containing no coloring agent, and the coating film is irradiated with electromagnetic waves and/or heated to obtain a transparent cured film or an insulating film. Such a cured film or an insulating film can be used, for example, as a planarizing film such as a liquid crystal display or an organic EL display, or as an interlayer insulating film.

Further, the cured film or the insulating film may be a pattern. As described above, by irradiating the coating film with an electromagnetic wave in a specific pattern and developing it, a patterned cured film or an insulating film can be obtained. The patterned cured film can be used, for example, as a spacer or a partition wall of a liquid crystal display or an organic EL display.

Further, a coating film may be formed by using a photosensitive resin composition containing a coloring agent (particularly, a photosensitive resin composition of a first aspect), and the coating film may be irradiated with electromagnetic waves in a specific pattern and developed. To form a pixel or black matrix of a color filter such as a liquid crystal display.

The display device of the present invention includes such a cured film, an insulating film, and a color filter. Examples of the display device include a liquid crystal display, an organic EL display, and the like.

[Examples]

Hereinafter, the examples are shown to further illustrate the present invention, but the scope of the present invention is not limited to the examples.

<Compound represented by the above formula (1) and comparative compound>

Compounds 1 to 2 represented by the following formulas are prepared as the compound represented by the above formula (1). The synthesis method of the compounds 1 to 2 is as follows. Further, Comparative Compounds 1 to 3 represented by the following formula were prepared for comparison.

[Synthesis of Compound 1]

First, 30 g of cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to methanol. Next, the methanol solution was stirred at 40 °C. Methanol was distilled off, and the residue was suspended in 200 g of water. To the resulting suspension, 200 g of tetrahydrofuran was mixed and stirred, and the aqueous phase was separated. to Under ice cooling, 4 g of hydrochloric acid was added and stirred, and then 100 g of ethyl acetate was mixed and stirred. After the mixture was allowed to stand, the oil phase was taken. The target was precipitated into crystals from the oil phase, and the precipitate was collected to obtain an imidazole compound (compound 1) having the above structure.

The results of ¹ H-NMR measurement of the imidazole compound (Compound 1) having the above structure are shown below.

¹ H-NMR (DMSO): 11.724 (s, 1H), 7.838 (s, 1H), 7.340 (d, 2H, J = 4.3 Hz), 7.321 (d, 1H, J = 7.2 Hz), 6.893 (d, 2H, J = 4.3 Hz), 6.876 (d, 1H, J = 6.1 Hz), 5.695 (dd, 1H, J = 4.3J, 3.2J), 3.720 (s, 3H), 3.250 (m, 2H)

[Synthesis of Compound 2]

An imidazole compound of the following structure was synthesized as the compound 2.

Specifically, the imidazole compound (compound 2) having the above-described structure was obtained in the same manner as the synthesis method of the compound 1, except that the starting compound was changed to the cinnamic acid derivative having the structure of the following formula.

<Preparation of photosensitive resin composition> [Example 1]

The following components are mixed and dissolved in a mixed solvent of 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60 / 20 / 20 (mass ratio) Among them, a negative photosensitive resin composition having a solid content concentration of 15% by mass was prepared.

‧ alkali soluble resin

Resin (A-1) (solid content 55%, solvent: 3-methoxybutyl acetate) ‧ ‧ 310 parts by mass

‧Photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA) ‧‧65 parts by mass

‧Photopolymerization initiator

"OXE-02" (trade name: BASF company) ‧ ‧ 15 parts by mass

‧ compounds represented by the above formula (1)

1‧‧‧5 parts by mass of the above compound

‧Colorant

Carbon dispersion "CF Black" (trade name: solid content 25% solvent manufactured by Yuki Co., Ltd.: 3-methoxybutyl acetate) ‧ ‧ 1200 parts by mass

The synthesis method of the above resin (A-1) is as follows.

First, a bisphenol oxime type epoxy resin (epoxy equivalent 235) 235 g, tetramethylammonium chloride 110 mg, 2,6-di-tert-butyl-4-methylphenol was placed in a 500 ml four-necked flask. 100 mg and 72.0 g of acrylic acid were blown into the air at a rate of 25 ml/min while being dissolved by heating at 90 to 100 °C. Next, the state in which the solution was turbid was gradually raised, and the mixture was heated to 120 ° C to be completely dissolved. At this point, the solution gradually became transparent and viscous and continued to maintain agitation. In the meantime, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It takes 12 hours for the acid price to reach the target value. Then, it was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-4) which was colorless, transparent and solid.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above bisphenolphthalein type epoxy acrylate obtained in this manner, and then dissolved, and then mixed with benzophenone tetracarboxylic dianhydride 80.5 g and brominated tetra Ethyl ammonium 1 g, slowly warmed up, and reacted at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

Further, the resin (A-1) corresponds to the compound represented by the above formula (a-1).

[Example 2, Comparative Examples 1 to 4]

A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the above compound 2, the comparative compounds 1 to 3 were used instead of the compound 1, or the compound 1 was not used.

[assessment]

The negative photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 4 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and prebaked at 90 ° C for 120 seconds to form a film. A coating film having a thickness of 1.0 μm. Next, a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used, and a negative mask having a line pattern of 20 μm was formed through the exposure pitch of 50 μm. The film is exposed to ultraviolet light. The exposure amount was set to four stages of 20, 40, 60, and 120 mJ/cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, and then baked at 230 ° C for 30 minutes to form a line pattern.

Similarly, the coating film was irradiated with ultraviolet rays by a negative mask having a line pattern of 2, 5, 10, and 20 μm at an exposure pitch of 50 μm . The exposure amount was set to 10 mJ/cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, and then baked at 230 ° C for 30 minutes to form a line pattern.

The OD measuring apparatus D-200II (manufactured by GretagMacbeth Co., Ltd.) was used for the formed line pattern, and the OD value per 1 μm of the film thickness was measured.

Moreover, the linearity of the pattern was evaluated by observing the line pattern by an optical microscope. The straightness of the pattern is evaluated as "good" for those who do not shake the edge of the line, and "bad" for those who are shaken.

Further, the pattern shape was observed by an optical microscope to evaluate the pattern adhesion. The pattern adhesion was not peeled off from the substrate, and those who formed the line pattern were evaluated as "good" and peeled off from the substrate, and those who did not form the line pattern were evaluated as "none".

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 1 to 4 below.

As is apparent from Tables 1 and 2, when the negative photosensitive resin composition of Examples 1 and 2 containing the compound 1 or 2 represented by the above formula (1) is used, a straight line can be formed even at a low exposure amount of 20 mJ/cm ² . Excellent line pattern. Further, even with a low exposure amount of 10 mJ/cm ² , the line pattern of 2 μm is in close contact with the substrate. Further, when the negative photosensitive resin compositions of Examples 1 to 2 were used, there was no development residue.

On the other hand, when the negative photosensitive resin compositions of Comparative Examples 1 to 3 containing Comparative Compounds 1 to 3 were used, Tables 3 and 4 show that The linearity and pattern adhesion were inferior to those of Examples 1 and 2, and good micropatterning properties could not be obtained.

In particular, the comparative compound 2 contained in the negative photosensitive resin composition of Comparative Example 2 is an amine-based decane coupling agent known as an adhesion enhancer, but at a low exposure amount of 10 mJ/cm ² , 20 μm The line pattern is also not in close contact with the substrate.

Further, the comparative compound 3 contained in the photosensitive resin composition of Comparative Example 3 has a hydroxyl group bonded to the ortho position of the benzene ring, but at a low exposure amount of 20 mJ/cm ² , only a poor linearity can be formed. Line pattern. Further, at a low exposure amount of 10 mJ/cm ² , only a line pattern of 10 μm or more is adhered to the substrate.

[Example 3]

The following components are mixed and dissolved in a mixed solvent of 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60 / 20 / 20 (mass ratio) Among them, a negative photosensitive resin composition having a solid content concentration of 15% by mass was prepared.

‧ alkali soluble resin

Resin (A-2) (glycidyl methacrylate / methacrylic acid / tricyclodecyl methacrylate = 72/18/10 (mass ratio), mass average molecular weight 14000) ‧ ‧ 166 parts by mass

‧Photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA) ‧ ‧ 33 parts by mass

‧Photopolymerization initiator

"OXE-02" (trade name: manufactured by BASF) ‧ ‧ parts by mass

‧ compounds represented by the above formula (1)

1‧‧1 1 parts by mass of the above compound

[Example 4, Comparative Examples 5 to 7]

A negative photosensitive resin composition was prepared in the same manner as in Example 3 except that the above compound 2 and the comparative compounds 1 to 3 were used instead of the compound 1.

[assessment]

The negative photosensitive resin compositions of Examples 3 to 4 and Comparative Examples 5 to 7 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and prebaked at 90 ° C for 120 seconds to form a film. A coating film having a thickness of 1.0 μm. Next, using a mirror projection alignment illuminator (product name: TME-150RTO, manufactured by Topcon Corporation), the coating film was irradiated with ultraviolet rays by a negative mask having a line pattern of 20 μm formed at an exposure pitch of 50 μm. The exposure amount was set to four stages of 20, 40, 60, and 120 mJ/cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, and then baked at 230 ° C for 30 minutes to form a line pattern.

Similarly, the coating film was irradiated with ultraviolet rays by a negative mask having a line pattern of 5, 10, and 20 μm formed at an exposure pitch of 50 μm. The exposure amount was set to 20 mJ/cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, and then baked at 230 ° C for 30 minutes to form a line pattern.

The linearity of the pattern was evaluated by observing the line pattern formed by an optical microscope. The straightness of the pattern is evaluated as "good" for those who do not shake the edge of the line, and "bad" for those who are shaken.

Further, the pattern shape was observed by an optical microscope to evaluate the pattern adhesion. The pattern adhesion was not peeled off from the substrate, and those who formed the line pattern were evaluated as "good" and peeled off from the substrate, and those who did not form the line pattern were evaluated as "none".

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 5 to 8 below.

As can be seen from Tables 5 and 6, when a negative photosensitive resin composition of Examples 3 to 4 containing Compound 1 or 2 represented by the above formula (1) is used, a straight line can be formed even at a low exposure amount of 20 mJ/cm ² . Excellent line pattern. Further, even with a low exposure amount of 20 mJ/cm ² , a line pattern of 5 μm is adhered to the substrate. Further, when the negative photosensitive resin compositions of Examples 3 to 4 were used, there was no development residue.

On the other hand, when the negative photosensitive resin compositions of Comparative Examples 5 to 7 containing Comparative Compounds 1 to 3 were used, it can be seen from Tables 7 and 8 that the pattern linearity and the pattern adhesion were both inferior to that in Example 3. ~4 difference, can not get good micro-patterning characteristics.

In particular, the comparative compound 2 contained in the negative photosensitive resin composition of Comparative Example 6 is an amine-based decane coupling agent known as an adhesion enhancer, but at a low exposure amount of 20 mJ/cm ² , 20 μm The line pattern is also not in close contact with the substrate.

Further, the comparative compound 3 contained in the negative photosensitive resin composition of Comparative Example 7 has a hydroxyl group bonded to the ortho position of the benzene ring, but can be formed only at a low exposure amount of 20 mJ/cm ² . Line pattern with poor linearity. Further, at a low exposure amount of 20 mJ/cm ² , only a line pattern of 10 μm or more is adhered to the substrate.

[Example 5]

50 parts by mass of a poly-p-hydroxystyrene (mass average molecular weight 2500), a copolymer of p-hydroxystyrene/styrene=85/15 (mole ratio) (mass average molecular weight 2500), 50 parts by mass, and a melamine resin 15 parts by mass of NIKALAC MW-100LM (manufactured by Sanwa Chemical Co., Ltd.) dissolved in 247 parts by mass of propylene glycol monomethyl ether acetate, and dissolved therein as α-(methylsulfonyloxyimino) as a photoacid generator 15 parts by mass of 1-phenylacetonitrile and 3.0 parts by mass of 2,3,3',4,4',5'-hexahydroxybenzophenone, and further adding the above compound 1 to give a mass of 3 in the solid component %, a negative photosensitive resin composition was prepared.

[Embodiment 6]

A negative photosensitive resin composition was prepared in the same manner as in Example 5 except that the above-mentioned compound 1 was added so as to be 8 mass% of the solid content.

[Embodiment 7]

In addition to the use of the above compound 2 in place of the above compound 1, A negative photosensitive resin composition was prepared in the same manner as in Example 5.

[Embodiment 8]

A negative photosensitive resin composition was prepared in the same manner as in Example 7 except that the compound 2 was added in an amount of 8% by mass.

[Comparative Example 8]

A negative photosensitive resin composition was prepared in the same manner as in Example 5 except that the above compound 1 was not added.

[assessment]

The negative photosensitive resin compositions of Examples 5 to 8 and Comparative Example 8 were applied onto a 6-inch substrate using a spinner, and dried on a hot plate at 110 ° C for 90 seconds to form a coating having a film thickness of 3.0 μm. membrane. Next, using a reduced projection exposure apparatus (product name: NSR-2005i10D, manufactured by Nikon Corporation), the coating film was selectively irradiated with i-line light through a negative mask formed with a line pattern of 0.55, 0.60, 0.65, and 0.70 μm. . The exposure amount was set to 100 mJ/cm ² . The exposed coating film was heated at 110 ° C for 90 seconds, and then developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 65 seconds, rinsed with water for 30 seconds, and then dried.

The pattern pattern formed was observed by a scanning electron microscope (SEM) to evaluate the pattern adhesion. Pattern adhesion, which is evaluated as "good", full stripping or partial stripping of the line full reproducer, resulting in a defect The assessment was "bad".

Further, the line pattern was observed by a scanning electron microscope (SEM), and the shape of the pattern was evaluated. The shape of the pattern is evaluated as "good" in the case where a rectangular pattern is formed on the substrate, and the tip of the pattern is tapered or the side is wavy.

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 9 and 10 below.

As is apparent from Tables 9 and 10, when the negative photosensitive resin composition of Examples 5 to 8 to which Compound 1 or 2 represented by the above formula (1) is added, a low exposure amount of 100 mJ/cm ² is 0.55 μm. The line pattern is also closely attached to the substrate, and the shape of the pattern is also excellent. Further, when the negative photosensitive resin compositions of Examples 5 to 8 were used, there was no development residue.

On the other hand, when the negative photosensitive resin composition of Comparative Example 8 in which the compound represented by the above formula (1) was not added, the pattern adhesiveness and the pattern shape were inferior to those of Examples 5 to 8, and it was not possible to obtain good results. The tiny graphical features.

[Embodiment 9]

35.0 g of a photosensitive polyimine precursor, 50.0 g of N-methylpyrrolidone, and 0.1 g (0.08 mmol) of p-methoxyphenol were stirred and mixed in a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube. It dissolves. Next, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole 2.0g (0.03mmol) and 2-mercaptobenzoxazole 1.0g (0.66) were added. Addition of the above compound 1 to the sensitizer of 0.2 g (0.06 mmol) of ethyl methoxide and 7.0 g (3.1 mmol) of 1,6-hexanediol diacrylate as an addition polymerizable compound The mixture was dissolved in a solid content of 3% by mass, dissolved at room temperature for a day and night, and then filtered through a filter to prepare a negative photosensitive resin composition.

The synthesis method of the above-mentioned photosensitive polyimine precursor is as follows.

1.30 g (0.010 mol) of 2-hydroxyethyl methacrylate was added to a stirred solution of 15.27 g (0.070 mol) of pyromellitic dianhydride in 100 ml of dry N-methylpyrrolidone under dry nitrogen. ester. The solution was stirred at room temperature for 1 hour, at 35 ° C for 1 hour, and then cooled to room temperature. The reaction solution was added dropwise to 8.49 g (0.040 mol) of 3,3'-dimethyl-4,4'-diaminobiphenyl and 0.25 g (0.001) in 100 ml of dry N-methylpyrrolidone. A stirred solution of a solution of 1,3-bis(3-aminopropyl)tetramethyldioxane was stirred for 1 hour and stirred at room temperature overnight. Thereafter, a solution of 26.82 g (0.130 mol) of N,N-dicyclohexylcarbodiimide in 100 ml of dry N-methylpyrrolidone was added dropwise to the reaction solution for 30 minutes while stirring. To the reaction solution, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred at 50 ° C for 5 hours, and stirred at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate after removing the unwanted matter by suction filtration was treated with 2.0 liter of ion-exchanged water under vigorous stirring. The precipitated solid is washed with ion-exchanged water, washed with methanol, and then suction-dried on a filter, and dried under reduced pressure at room temperature until the water content is less than 1.0% by mass to obtain a photosensitive polyimine. Precursor.

[Embodiment 10]

A negative photosensitive resin composition was prepared in the same manner as in Example 9 except that the above-mentioned compound 1 was added in an amount of 8% by mass.

[Example 11]

A negative photosensitive resin composition was prepared in the same manner as in Example 9 except that the above compound 2 was used instead of the above compound 1.

[Embodiment 12]

A negative photosensitive resin composition was prepared in the same manner as in Example 11 except that the compound 2 was added in an amount of 8% by mass.

[Comparative Example 9]

A negative photosensitive resin composition was prepared in the same manner as in Example 9 except that the above compound 1 was not added.

[assessment]

The negative photosensitive resin compositions of Examples 9 to 12 and Comparative Example 9 were spin-coated on a 6-inch substrate and dried to form a coating film of 5.0 ± 1.0 μm. Next, using a mirror projection alignment illuminator (product name: MPA-600FA, manufactured by Canon Co., Ltd.), the coating film was irradiated with ultraviolet rays through a negative mask formed with a line pattern of 6.0, 6.5, 7.0, and 8.0 μm. The exposure amount was set to 500 mJ/cm ² . Then, after standing in a light-shielded box for 1 hour, it was heated at 120 ° C for 60 seconds with a hot plate. Thereafter, paddle development was carried out using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to remove 1.2 times the development time required for the unexposed portion, followed by washing with water and drying.

The pattern pattern formed was observed by a scanning electron microscope (SEM) to evaluate the pattern adhesion. The pattern adhesion is evaluated as "good", all peeling or partial peeling of the line full reproducer, and the defect is evaluated as "bad".

Also, the scanning line electron microscope (SEM) was used to observe the line pattern and evaluate Graphic shape. The shape of the pattern is evaluated as "good" in the case where a rectangular pattern is formed on the substrate, and the tip of the pattern is tapered or the side is wavy.

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 11 and 12 below.

As can be seen from Tables 11 and 12, when the negative photosensitive resin composition of Examples 9 to 12 to which Compound 1 or 2 represented by the above formula (1) was added, a line pattern of 6.0 μm was adhered to the substrate, and The shape is also excellent. Further, when the negative photosensitive resin compositions of Examples 9 to 12 were used, there was no development residue.

On the other hand, when the negative photosensitive resin composition of Comparative Example 9 in which the compound represented by the above formula (1) was not added, the pattern adhesiveness and the pattern shape were inferior to those of Examples 9 to 12, and it was not good. The tiny graphical features.

[Example 13]

100 parts by mass of the polyimide precursor, 15 parts by mass of the above compound 1, and 843 parts by mass of N-methyl-2-pyrrolidone were mixed to prepare a negative photosensitive resin composition.

The synthesis method of the above polyimine precursor is as follows.

10.0 g (50 mmol) of bis(4-aminophenyl)ether was placed in a 300 mL 3-neck flask, and dissolved in 105.4 mL of dehydrated N,N-dimethylacetamide (DMAc) under a nitrogen stream. Stir in the ice bath while cooling. 14.7 g (50 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added thereto a little at a time, and after the addition was completed, the mixture was stirred in an ice bath for 5 hours, and the solution was dehydrated. The diethyl ether was reprecipitated, and the precipitate was dried under reduced pressure at room temperature for 17 hours to quantitatively obtain a white solid of a polyamine (polyimine precursor) having a mass average molecular weight of 10,000.

[Example 14 and Comparative Examples 10 to 11]

A negative photosensitive resin composition was prepared in the same manner as in Example 13 except that the above compound 2 and the comparative compounds 2 and 3 were used instead of the above compound 1.

[assessment]

The negative photosensitive resin compositions of Examples 13 to 14 and Comparative Examples 10 to 11 were spin-coated on a chrome-plated glass substrate so as to have a final film thickness of 4 μm, and dried on a hot plate at 80 ° C for 10 minutes. Coating film. Next, using a mirror projection alignment illuminator (product name: MPA-600FA, manufactured by Canon Co., Ltd.), the coating film was irradiated with ultraviolet rays through a negative mask formed with a line pattern of 20 μm. The exposure amount was set to 5 stages of 200, 300, 400, and 500 mJ/cm ² . The exposed coating film was heated on a hot plate at 140 ° C for 10 minutes (heating after exposure), and then immersed in a volume ratio of 2.38 mass% aqueous tetramethylammonium hydroxide and isopropyl alcohol in a volume ratio of 9:1. The developer was developed, and post-baked at 350 ° C for 1 hour to carry out hydrazine imidization to form a line pattern.

The pattern pattern formed was observed by a scanning electron microscope (SEM) to evaluate pattern formation. The pattern formation is evaluated as "good", all stripped or partially peeled off, and the defect is evaluated as "poor".

Moreover, the linearity of the pattern was evaluated by observing the line pattern by an optical microscope. The straightness of the pattern is evaluated as "good" for those who do not shake the edge of the line, and "bad" for those who are shaken.

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 13 and 14 below.

In the case of using the negative photosensitive resin composition of Examples 13 to 14 containing the compound 1 or 2 represented by the above formula (1), it can be seen that the pattern shape can be formed at a low exposure amount of 200 mJ/cm ² . Excellent 20 μm line pattern with excellent linearity at a low exposure of 300 mJ/cm ² . Further, when the negative photosensitive resin compositions of Examples 13 to 14 were used, there was no development residue.

On the other hand, when the negative photosensitive resin composition of Comparative Examples 10 to 11 which does not contain the compound represented by the above formula (1) was used, the pattern formation property and the pattern linearity were inferior to those of Examples 13 to 14, and it was impossible to Get good micro-patterning properties.

[Example 15]

Mix 100 parts by mass of epoxy resin (YP50EK35 (phenoxy tree) A negative photosensitive resin composition was prepared from the above-mentioned compound 1 in an amount of 10 parts by mass of the above-mentioned compound 1 and a resin (manufactured by Nippon Steel Chemical Co., Ltd.).

[Example 16 and Comparative Examples 12 to 13]

A negative photosensitive resin composition was prepared in the same manner as in Example 15 except that the above compound 2 and the comparative compounds 2 and 3 were used instead of the above compound 1.

[assessment]

The negative photosensitive resin compositions of Examples 15 to 16 and Comparative Examples 12 to 13 were spin-coated on a glass substrate so as to have a final film thickness of 0.5 μm , and dried on a hot plate at 80 ° C for 15 minutes. Coating film. Next, using a mirror projection alignment illuminator (product name: MPA-600FA, manufactured by Canon Co., Ltd.), the coating film was irradiated with ultraviolet rays through a negative mask formed with a line pattern of 20 μm. The exposure amount was set to 5 stages of 70, 80, 90, and 100 mJ/cm ² . The exposed coating film was heated (heated after exposure) on a hot plate at 150 ° C for 30 minutes, and then immersed in a developing solution in which isopropyl alcohol and chloroform were mixed at a volume ratio of 4:1 to develop a line pattern. .

The pattern pattern formed was observed by a scanning electron microscope (SEM) to evaluate pattern formation. The pattern formation is evaluated as "good", all stripped or partially peeled off, and the defect is evaluated as "poor".

Moreover, the linearity of the pattern was evaluated by observing the line pattern by an optical microscope. The linearity of the pattern is evaluated as "good" by the person who does not shake the edge of the line. The shaker evaluates as "bad."

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 15 and 16 below.

As can be seen from Tables 15 and 16, when the negative photosensitive resin composition of Examples 15 to 16 containing the compound 1 or 2 represented by the above formula (1) is used, it can be formed at 70 mJ/cm without heating after exposure. excellent pattern shape at a low exposure amount of ² at 80mJ / cm excellent linearity of 20μm line pattern at the exposure amount of ^2. Further, when the negative photosensitive resin compositions of Examples 15 to 16 were used, there was no development residue.

On the other hand, when the negative photosensitive resin composition of Comparative Examples 12 to 13 which does not contain the compound represented by the above formula (1) was used, the pattern formation property and the pattern linearity were inferior to those of Examples 15 to 16. Get good Tiny graphic features.

[Example 17]

A negative photosensitive resin composition was prepared by kneading the following components (mass parts in terms of solid content) in a three-roll mill.

‧Epoxy-containing polycarboxylic acid resin

Resin (F-1) ‧ ‧ ‧ 58.3 parts by mass

‧Photoacid generator

"PCI-220" (trade name: manufactured by Nippon Kayaku Co., Ltd.) ‧ ‧ 4.2 parts by mass

‧ compounds represented by the above formula (1)

1‧‧‧4 parts by mass of the above compound

‧ Sensitizer

2-ethyl-9,10-dimethoxyfluorene ‧ ‧ 0.4 parts by mass

‧modified ingredients

"YX-4000" (trade name: manufactured by Yuka Shell Epoxy Co., Ltd., epoxy compound) ‧ ‧ ‧ 25.1 parts by mass

"Cymel300" (trade name: melamine resin manufactured by Cytec, Japan) ‧‧11.7 parts by mass

‧Filling agent

"Silbond 800EST" (trade name: white stone calcium company, surface treatment spherical cerium oxide) ‧ ‧ 25.0 parts by mass

"B-30" (trade name: 堺Chemical Industry Co., Ltd., barium sulfate) ‧‧25.0 parts by mass

"SG-2000" (trade name: made by Japan Talc, talc) ‧ ‧ 5.8 parts by mass

‧additive

"Heliogen Green" (trade name: Yamamoto Co., Ltd., pigment) ‧ ‧ ‧ 1.4 parts by mass

"BYK-354" (trade name: BYK company, leveling agent) ‧ ‧ 1.6 parts by mass

"BYK-057" (trade name: BYK company, defoamer) ‧ ‧ 1.6 parts by mass

The synthesis method of the above resin (F-1) is as follows.

Epoxy resin (Nippon Chemical Co., Ltd., NC-3000PL, epoxy equivalent 274, softening point 57.3 ° C) obtained by reacting biphenyl dimethylene-hydroxy benzene with epichlorohydrin was added to 211.2 g, 72.4 g of hydroxymethylpropionic acid, 70.9 g of carbitol acetate, and 0.71 g of triphenylphosphine were heated at 100 ° C until the acid value of the reaction liquid became 1 mgKOH/g or less. The reaction time was 24 hours. Then, 0.51 g of Percumyl H80 (manufactured by NOF Corporation, peroxide) was added to the reaction mixture, and the mixture was stirred for about 2 hours to oxidize triphenylphosphine of the reaction catalyst to deactivate it. Thereafter, 66.4 g of tetrahydrophthalic anhydride and 117.6 g of carbitol acetate were added, and the mixture was reacted at 95 ° C for 4 hours to obtain a resin (F-1). The acid value of the resin (F-1) was 70 mgKOH/g.

[Embodiment 18]

In addition to using the above compound 2, respectively, in place of the above compound 1 A negative photosensitive resin composition was prepared in the same manner as in Example 17.

[Comparative Example 14]

A negative photosensitive resin composition was prepared in the same manner as in Example 17 except that the above compound 1 was not blended.

[Comparative Example 15]

The blending amount of the resin (F-1) was 57.9 parts by mass, and the blending amount of 2-ethyl-9,10-dimethoxyanthracene was 0.8 parts by mass, and the blending amount of "Cymel300" was A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 14, except that the amount was 11.6 parts by mass.

[Comparative Example 16]

In addition, the blending amount of the resin (F-1) was 57.0 parts by mass, and the blending amount of "PCI-220" was 4.1 parts by mass, and the blend of 2-ethyl-9,10-dimethoxyanthracene was blended. A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 14, except that the amount of the "Cymel 300" was 11.4 parts by mass.

[assessment]

The negative photosensitive resin compositions of Examples 17 to 18 and Comparative Examples 14 to 16 were coated on the entire surface by a screen printing method using a 100 mesh stainless steel screen so as to have a thickness of 25 μm. A copper clad laminate having a pattern was used, and the coating film was dried in a hot air dryer at 80 ° C for 30 minutes. Then, a quartz mask having a line pattern of 40 μm, 45 μm, 50 μm, and 60 μm was adhered to the coating film, and the coating film was irradiated with ultraviolet rays using an ultraviolet exposure apparatus (product name: EXM-1066, manufactured by ORC Manufacturing Co., Ltd.). The exposure amount was set to 500 mJ/cm ² . Subsequently, after the post-exposure baking treatment with a hot air dryer, it was developed with a 1% sodium carbonate aqueous solution at 25 ° C and a spray pressure of 2 kg/cm ² for 60 seconds to dissolve and remove the unexposed portion. Thereafter, the film was heat-hardened by a hot air dryer at 150 ° C for 60 minutes.

The pattern pattern formed was observed by a scanning electron microscope (SEM) to evaluate the pattern adhesion. The pattern adhesion is evaluated as "good", all peeling or partial peeling of the line full reproducer, and the defect is evaluated as "bad".

Further, the line pattern was observed by a scanning electron microscope (SEM), and the shape of the pattern was evaluated. The shape of the pattern is evaluated as "good" for a penetrator that is rectangular in shape and that is not tapered or developed, and is evaluated as "poor" by a cone or developer.

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 17 and 18 below.

As can be seen from Tables 17 and 18, when the negative photosensitive resin composition of Examples 17 to 18 containing the compound 1 or 2 represented by the above formula (1) was used, a line pattern of 40 μm was adhered to the substrate, and the shape of the pattern was obtained. Also excellent. Further, when the negative photosensitive resin compositions of Examples 17 to 18 were used, there was no development residue.

On the other hand, when the negative photosensitive resin compositions of Comparative Examples 15 to 16 which were not blended with the compound represented by the above formula (1) were used, the pattern adhesion and the pattern shape were inferior to those of Examples 17 to 18. Unable to get good micro-patterning features.

[Embodiment 19]

The following components were mixed and dissolved in a mixed solvent of methyl ethyl diglycol/propylene glycol monomethyl ether acetate = 40/60 (mass ratio) to prepare a negative photosensitive resin composition having a solid concentration of 15% by mass. .

‧ alkali soluble resin

Resin (A-3) (4-oxatetracycline-[6.2.1.0 ^2,7 0 ^3,5 ]undecyl(meth)acrylate/methacrylic acid/tricyclodecyl methacrylate=72 /18/10 (mass ratio), mass average molecular weight 14000) ‧ ‧ 166 parts by mass

‧Photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA) ‧ ‧ parts by mass

‧Photopolymerization initiator

Starting agent 1 (combined from the following Synthesis Examples 1 to 3, the oxime ester compound 1 represented by the following formula) ‧ ‧ ‧ parts by mass

‧ compounds represented by the above formula (1)

1‧‧1010 parts by mass of the above compound

‧additive

Carboxybenzotriazole ‧ ‧ parts by mass

[Synthesis Example 1] (Synthesis of 9,9-di-n-propyl hydrazine)

6.64 g (40 mmol) of hydrazine was dissolved in 27 mL of tetrahydrofuran (THF). Under a nitrogen atmosphere, 0.12 g (1.1 mmol) of tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of a sodium hydroxide aqueous solution having a concentration of 50% by mass were gradually added to the obtained solution. Will The resulting mixture was stirred at 80 ° C for 3 hours to carry out a reaction. After adding 33 g of ethyl acetate and 33 g of water to the mixture after the reaction, the mixture was separated into an organic layer and an aqueous layer. After the obtained organic layer was dried over anhydrous sodium sulfate, solvent was removed from the organic layer using a rotary evaporator to obtain 9.32 g (yield: 83%) of 9,9-di-n-propylhydrazine.

[Synthesis Example 2]

9.10 g (16.37 mmol) of 9,9-di-n-propyl hydrazine and 3.04 g (18.00 mmol) of (2-methylphenyl)acetic acid chloride in the presence of 2.62 g of aluminum chloride. The reaction was carried out for 1 hour under ice cooling in 50 ml of a chloromethane solvent. The reaction mixture was poured into ice water, and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate and evaporated. The residue was purified by a cerium oxide gel column with an ethyl acetate/hexane = 1/2 solution to obtain 2-(2-methylphenyl)ethyl fluorenyl-9,9-di-n-propyl The base is 5.95 g (15.55 mmol). 2-(2-Methylphenyl)ethyl fluorenyl-9,9-di-n-propyl hydrazine 5.95 g (15.55 mmol), with concentrated hydrochloric acid 1.60 g (15.55 mmol), isobutyl nitrite 2.42 In the presence of g (23.33 mmol), it was reacted in 25 ml of dimethylformamide solvent for 3 hours under ice cooling. The reaction mixture was evaporated, and ethyl acetate was added to the residue, and the mixture was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated to give 2-[2-methylphenyl (hydroxyimino)ethyl hydrazide. ]-9,9-di-n-propyl oxime 4.80 g (11.67 mmol).

The results of ¹ H-NMR measurement of 2-[2-methylphenyl(hydroxyimino)ethenyl]-9,9-di-n-propylhydrazine are shown below.

¹ H-NMR (600MHz, CDCl ₃ , ppm): 8.60 (bs, 1H), 8.15 (d, 1H), 8.14 (s, 1H), 7.76-8.00 (m, 2H), 7.26-7.53 (m, 7H) ), 2.35 (s, 3H), 1.98-2.01 (m, 4H), 0.63-0.67 (m, 10H)

[Synthesis Example 3]

2-[2-Methylphenyl(hydroxyimino)ethenyl]-9,9-di-n-propylindole 4.80 g (11.67 mmol), acetic anhydride 1.43 g (13.42 mmol), triethyl 1.36 g (13.42 mmol) of an amine was mixed with 45.00 ml of dimethylformamide solvent, and stirred at 35 ° C for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction mixture, which was washed with water, dried over anhydrous magnesium sulfate and evaporated. The residue was purified by a cerium oxide gel column using an ethyl acetate/hexane = 2/1 solution to obtain 4.76 g (10.50 mmol, yield 72%) of the oxime ester compound 1.

The results of ¹ H-NMR measurement of the oxime ester compound 1 are shown below.

^{1 H-NMR (600MHz, CDCl} 3, ppm): 8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7.33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (m, 4H), 0.63-0.66 (m, 10H)

[assessment]

The negative photosensitive resin composition of Example 18 was applied onto a copper substrate using a spin coater, and prebaked at 90 ° C for 120 seconds to form a coating film having a film thickness of 1.0 μm . Next, using a mirror projection alignment exposer (product name: TME-150RTO, manufactured by Topcon Corporation), the coating film was irradiated with ultraviolet rays through a negative mask having a line pattern of 20 μm at an exposure pitch of 50 μm . . The exposure amount was set to four stages of 20, 40, 60, and 120 mJ/cm ² . The exposed coating film was developed with a 2.38 mass% TMAH aqueous solution at 23 ° C for 40 seconds, and then baked at 230 ° C for 30 minutes to form a line pattern.

Similarly, the coating film was irradiated with ultraviolet rays by a negative mask having a line pattern of 5, 10, and 20 μm formed at an exposure pitch of 50 μm. The exposure amount was set to 20 mJ/cm ² . The exposed coating film was developed with a 2.38 mass% TMAH aqueous solution at 23 ° C for 40 seconds, and then baked at 230 ° C for 30 minutes to form a line pattern.

The linearity of the pattern was evaluated by observing the line pattern formed by an optical microscope. The straightness of the pattern is evaluated as "good" for those who do not shake the edge of the line, and "bad" for those who are shaken.

Further, the pattern shape was observed by an optical microscope to evaluate the pattern adhesion. The pattern adhesion was not peeled off from the substrate, and those who formed the line pattern were evaluated as "good" and peeled off from the substrate, and those who did not form the line pattern were evaluated as "none".

Further, the presence or absence of residue in the unexposed portion after development was evaluated.

The results are shown in Tables 19 to 20 below.

In the case of using the negative photosensitive resin composition of Example 19 containing the compound 1 represented by the above formula (1) on the copper substrate, it is possible to form a linear property with a low exposure amount of 20 mJ/cm ² . Line pattern. Further, even with a low exposure amount of 20 mJ/cm ² , a line pattern of 5 μm is adhered to the substrate. Further, when the negative photosensitive resin composition of Example 19 was used, there was no development residue.

Claims (11)

A photosensitive resin composition containing a compound represented by the following formula (1), (In the formula (1), R ¹ is a hydrogen atom or an alkyl group, R ² is an aromatic group which may have a substituent, R ³ is an alkylene group which may have a substituent, and R ⁴ each independently represents a halogen atom; Hydroxy, mercapto, thioether, decyl, decyl, nitro, nitroso, sulfonate, phosphino, phosphinyl, phosphonate, or organic, n is an integer from 0 to 3) . The photosensitive resin composition of claim 1, further comprising a resin selected from the group consisting of a resin having a cardo structure, a resin having a phenolic hydroxyl group, a polyimide resin, and an epoxy resin. The photosensitive resin composition of claim 1, further comprising an alkali-soluble resin, a photopolymerization initiator, and an organic solvent. The photosensitive resin composition of claim 3, which further contains a photopolymerizable monomer. The photosensitive resin composition of claim 3 or 4, which further contains a colorant. The photosensitive resin composition of claim 5, wherein the colorant is an opacifier. A pattern forming method, which is used as claimed in claims 1 to 6 In one photosensitive resin composition, a coating film or a molded body is formed, and the coating film or the molded body is irradiated with electromagnetic waves in a specific pattern and developed. A cured film formed using the photosensitive resin composition according to any one of claims 1 to 4. An insulating film formed using the photosensitive resin composition according to any one of claims 1 to 4. A color filter formed using the photosensitive resin composition of claim 5 or 6. A display device comprising a cured film as claimed in claim 8, an insulating film as claimed in claim 9, or a color filter as in claim 10.