KR102522739B1 - Photosensitive resin composition, pattern forming method, cured film, insulating film, color filter, and display device - Google Patents

Abstract

(식 (1) 중, R¹ 은 수소 원자 또는 알킬기이고, R² 는 치환기를 가져도 되는 방향족기이고, R³ 은 치환기를 가져도 되는 알킬렌기이고, R⁴ 는, 각각 독립적으로 할로겐 원자, 수산기, 메르캅토기, 술파이드기, 실릴기, 실란올기, 니트로기, 니트로소기, 술포나토기, 포스피노기, 포스피닐기, 포스포나토기, 또는 유기기이고, n 은 0 ∼ 3 의 정수이다.) [Problem] A negative photosensitive resin composition capable of forming a pattern with excellent adhesion at a low exposure amount, a pattern formation method using the negative photosensitive resin composition, a cured film formed using the negative photosensitive resin composition, an insulating film, and a color filter, And a display device provided with the cured film, the insulating film, or the color filter is provided.
[Solution] A negative photosensitive resin composition containing a compound represented by the following formula (1).

(In 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, R ⁴ is each independently a halogen atom, A hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n is an integer of 0 to 3 am.)

Description

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

A photosensitive resin composition, a pattern formation method using the photosensitive resin composition, a cured film formed using the photosensitive resin composition, an insulating film, and a color filter, and a display device comprising the cured film, insulating film, or color filter It is about.

The negative photosensitive resin composition in the photosensitive resin composition has a characteristic of being cured by irradiation of electromagnetic waves such as ultraviolet rays. This negative photosensitive resin composition is widely used in various applications such as display devices, semiconductor devices, electronic components, and microelectromechanical systems (MEMS) because a pattern having a desired shape can be obtained by curing a portion irradiated with electromagnetic waves. For example, in a display device, it is used as a material for a flattening film, an insulating film, a color filter, a black matrix, a spacer, a barrier rib, or the like in a liquid crystal display or an organic EL display. Also in the case of a positive photosensitive resin composition, a cured product can be obtained by a process such as heat curing obtained after irradiation with electromagnetic waves such as ultraviolet rays and development.

In such a photosensitive resin composition, in order to ensure product reliability, high adhesion to a substrate is required even when a minute pattern is formed. Therefore, conventionally, a photosensitive resin composition containing an amine-based silane coupling agent as an adhesion enhancer has been proposed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2000-035670

By the way, in recent years, a photosensitive resin composition capable of forming a pattern of a good shape with a low exposure amount has been desired from the viewpoint of further productivity improvement.

However, when an amine-based silane coupling agent is incorporated as an adhesion enhancer as in Patent Document 1, the adhesion to the substrate is improved, but there is a problem that the amount of exposure required for pattern formation increases.

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

The inventors of the present invention repeated intensive research in order to achieve the above object. As a result, they discovered that the said subject could be solved by containing a specific compound in the photosensitive resin composition, and came to complete this invention. Specifically, the present invention provides the following.

The 1st aspect of this invention is the photosensitive resin composition containing the compound represented by following formula (1).

[Formula 1]

(In 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, R ⁴ is each independently a halogen atom or a hydroxyl group , mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, or an organic group, and n is an integer of 0 to 3 .)

The second aspect of the present invention is a pattern formation method in which a coated film or molded body is formed using the photosensitive resin composition according to the present invention, and the coated film or molded body is irradiated with electromagnetic waves in a predetermined pattern and developed.

The 3rd aspect of this invention is a cured film formed using the photosensitive resin composition which concerns on this invention.

A fourth aspect of the present invention is an insulating film formed using the photosensitive resin composition according to the present invention.

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

A sixth aspect of the present invention is a display device provided with a cured film, an insulating film, or a color filter according to the present invention.

According to the present invention, a photosensitive resin composition capable of forming a pattern having excellent adhesion with a low exposure amount, a pattern formation method using the photosensitive resin composition, a cured film, an insulating film, and a color filter formed using the photosensitive resin composition, and a cured film thereof , an insulating film, or a display device having a color filter.

<<Photosensitive Resin Composition>>

In this 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 this invention is a photosensitive resin composition containing the compound represented by following formula (1). Below, the compound represented by Formula (1) is demonstrated first, and then the photosensitive resin composition is demonstrated.

[Formula 2]

(In 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, R ⁴ is a halogen atom, a hydroxyl group, mer A capto group, a sulfide 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 from 0 to 3.)

In 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 straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

Specific examples of the alkyl group preferred as R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and isophene. ethyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group. can

In 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 an aromatic heterocyclic group which may have a substituent.

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

The type of aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzooxazolyl group, and a benzothiazolyl group. group, and a benzoimidazolyl group are preferred.

Examples of substituents that the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, and a sulfone group. groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonato groups, amino groups, ammonio groups, and organic groups. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an 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, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may include a bond other than a hydrocarbon group such as a hetero atom or a substituent in the organic group. Moreover, any of a linear form, a branched chain form, and a cyclic form may be sufficient as this organic group. This organic group is usually monovalent, but can be a divalent or higher valent organic group in the case of forming a cyclic structure or the like.

When an aromatic group has a substituent on the adjacent carbon atom, two substituents bonded on the adjacent carbon atom may be bonded to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

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

As the bond containing the hetero atom that the organic group may have, from the viewpoint of the heat resistance of the compound represented by formula (1), ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, amino Bond (-NR-: R represents a hydrogen atom or a monovalent organic group) Urethane bond, imino bond (-N=C(-R)-, -C(=NR)-: R is a hydrogen atom or a monovalent organic group group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond are preferable.

When the organic group is a substituent other than a hydrocarbon group, the type of substituent other than a hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of substituents other than hydrocarbon groups include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, and an isothiocyanato group. , silyl group, silanol group, alkoxy group, alkoxycarbonyl group, amino group, monoalkylamino group, dialkyl aluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate , Acyl group, acyloxy group, sulfino group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, alkyl ether group, alkenyl ether group, alkylthio ether group, alkenyl thio ether group, aryl ether group, arylthio ether group, etc. are mentioned. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. Moreover, the hydrocarbon group contained in the said substituent may be any of linear, branched chain, and cyclic|annular.

Examples of the substituent of the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group include an alkyl group of 1 to 12 carbon atoms, an aryl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, and An aryloxy group of 1 to 12, an arylamino group of 1 to 12 carbon atoms, and a halogen atom are preferable.

As R ² , the compound represented by formula (1) can be synthesized inexpensively and easily, and since the solubility of the imidazole compound in water and organic solvents is good, a phenyl group, a furyl group, or a thienyl group each of which may have a substituent Giga is preferred.

In Formula (1), R ³ is an alkylene group which may have a substituent. Substituents that the alkylene group may have are not particularly limited as long as the object of the present invention is not impaired. As a specific example of the substituent which an alkylene group may have, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom, etc. are mentioned. The alkylene group may be a straight-chain alkylene group or a branched-chain alkylene group, and a straight-chain alkylene group is preferable. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 20, preferably 1 to 10, and more preferably 1 to 5. In addition, the number of carbon atoms in the alkylene group does not include carbon atoms of substituents bonded to the alkylene group.

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

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

Specific examples of the alkylene group preferred as R ³ include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, n-butane- 1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl group , n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tree Decane-1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane- 1,17-diyl group, n-octadecane-1,18-diyl group, n-nonadecane-1,19-diyl group, and n-icosan-1,20-diyl group.

R ⁴ is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group; n is an integer of 0-3. 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 for R ² .

When R ⁴ is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. As the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable. Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, and a benzothiazolyl group. group, and a benzoimidazolyl group are preferred, and a furyl group and a thienyl group are more preferred.

When R ⁴ is an alkyl group, the position at which the alkyl group is bonded to the imidazole ring is preferably at the 2nd position, 4th position or 5th position, and more preferably at the 2nd position. When R ⁴ is an aromatic hydrocarbon group or an aromatic heterocyclic group, the bonding position of these groups on the imidazole is preferably at the 2nd position.

Among the compounds represented by the above formula (1), the compound represented by the following formula (1-1) is preferable because it is inexpensive and easily synthesizable and has excellent solubility in water and organic solvents. ) and a compound in which R ³ is a methylene group is more preferable.

[Formula 3]

(In formula (1-1), R ¹ , R ³ , R ⁴ , and n are the same as in 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, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group, provided that 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 organic groups, the organic group is the same as the organic group that R ² in Formula (1) has as a substituent. R ⁵ , R ⁶ , R ⁷ , and R ⁸ are preferably hydrogen atoms in view of the solubility of the imidazole compound in a solvent.

Among them, R ⁵ , R ⁶ , R ⁷ , R ⁸ , And at least one of R ⁹ is preferably the following substituent, and it is particularly preferable that R ⁹ is the following substituent. When R ⁹ is a substituent shown below, it is preferable that R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen atoms.

-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 that R ² in Formula (1) has as a substituent. As ^R10 , an alkyl group is preferable, a C1-C8 alkyl group is more preferable, a C1-C3 alkyl group is especially preferable, and a methyl group is most preferable.

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

[Formula 4]

(In formula (1-1-1), R ¹ , R ⁴ , and n are the same as in formula (1), and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently , Hydrogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phos A phonato group, an amino group, an ammonio group, or an organic group, provided that 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 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 -OR 10 described above, and R ¹⁵ is -OR Groups represented by ¹⁰ are particularly preferred. When R ¹⁵ is a group represented by -OR ¹⁰ , it is preferable that R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen atoms.

The synthesis method of the compound represented by said formula (1) is not specifically limited. For example, the above formula (1 ) can be synthesized.

[Formula 5]

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

In addition, when the imidazole compound is a compound represented by formula (1) and R ³ is a methylene group, that is, when the imidazole compound is a compound represented by formula (1-1) below, to the Michael addition reaction described below An imidazole compound can also be synthesized by the method described above.

[Formula 6]

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

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

[Formula 7]

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

Moreover, the imidazole compound represented by following formula (1-3) is obtained by adding the 3-substituted acrylic acid derivative containing an imidazolyl group represented by following formula (IV) in the solvent containing water.

[Formula 8]

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

In this case, the imidazole compound represented by the 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 formula (IV). Then, a Michael addition reaction occurs between the 3-substituted acrylic acid represented by the formula (V) below and the imidazole compound represented by the formula (II), and the imidazole compound represented by the formula (1-3) is produced.

[Formula 9]

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

The following are mentioned as a preferable specific example of the compound represented by Formula (1).

[Formula 10]

The compound represented by the above formula (1) has good solubility in organic solvents, and when incorporated in the photosensitive resin composition, good micropatterning properties can be obtained.

In addition, this compound can be synthesized in the same manner as in the Examples described later.

<Photosensitive resin composition>

As the photosensitive resin composition related to the present invention, a conventionally known photosensitive resin composition in which the compound represented by the formula (1) is added can be used without particular limitation. Hereinafter, specific examples of the photosensitive resin composition according to the present invention will be described in detail.

In addition, although not limited to the following specific examples, it is preferable that the photosensitive resin composition has a compound represented by the formula (1), an alkali-soluble resin, a photopolymerization initiator or photosensitizer, and an organic solvent. You may use a photopolymerizable monomer as needed.

Examples of the alkali-soluble resin include conventionally known resins having an alkali-soluble group such as a carboxyl group, a phenol 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, a (hydroxy)styrene resin, or polysiloxane or polysilane. The silicon-containing resin of, etc. are mentioned. As the alkali-soluble resin, it is preferable to contain 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. Details of the photopolymerization initiator or photosensitizer, organic solvent, and photopolymerizable monomer are also described in the photosensitive resin compositions of the first to seventh aspects described later.

(1) The 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 formula (1), and an organic solvent.

It does not specifically limit as alkali-soluble resin in the photosensitive resin composition of a 1st aspect, Conventionally well-known alkali-soluble resin can be used. This alkali-soluble resin may have an ethylenically unsaturated group or may not have an ethylenically unsaturated group.

In addition, in this specification, an alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and 2.38% by mass of tetra It refers to dissolving in a film thickness of 0.01 µm or more when immersed in an aqueous solution of methyl ammonium hydroxide (TMAH) for 1 minute.

As alkali-soluble resin which has an ethylenically unsaturated group, resin obtained by making the reactant of an epoxy compound and an unsaturated carboxylic acid further react with a polybasic acid anhydride can be used, for example.

Especially, resin represented by the following formula (a-1) is preferable. The resin represented by this formula (a-1) is preferable in terms of its high photocurability.

[Formula 11]

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

[Formula 12]

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, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a is , a single bond or a group represented by the following formula (a-3).

[Formula 13]

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 dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic acid anhydride, and methyltetrahydrophthalic anhydride. A phthalic acid, glutaric acid anhydride, etc. are mentioned.

In addition, in said formula (a-1), Z ^<a> represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

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

Moreover, polyester (meth)acrylate obtained by making (meth)acrylic acid react with the polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid as alkali-soluble resin which has an ethylenically unsaturated group; Polyurethane (meth)acrylate obtained by making (meth)acrylic acid react after making a polyol and the compound which has two isocyanate groups react; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol Epoxy (meth)acrylate resins obtained by reacting (meth)acrylic acid with epoxy resins such as polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins can also be used. .

In addition, in this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth)acrylate" means both an acrylate and a methacrylate.

On the other hand, as the alkali-soluble resin having no ethylenically unsaturated group, a resin obtained by copolymerizing at least an unsaturated carboxylic acid with an epoxy group-containing unsaturated compound having no alicyclic group and an alicyclic group-containing unsaturated compound can be used.

Examples of unsaturated carboxylic acids 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; anhydrides of these dicarboxylic acids; etc. can be mentioned. Among these, (meth)acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of resin obtained, ease of availability, and the like. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

As the epoxy group-containing unsaturated compound having no alicyclic group, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxy (Meth) such as heptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 4-oxatetracyclo-[6.2.1.0 ^2,7 0 ^3,5 ]undecanyl (meth)acrylate acrylic acid epoxy alkyl esters; α-alkyl acrylic acid epoxyalkyl esters such as α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and α-ethyl 6,7-epoxyheptyl acrylate; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; etc. can be mentioned. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, o - Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferable. These epoxy group-containing unsaturated compounds can 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 monocyclic or multicyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned. Specifically, as an alicyclic group-containing unsaturated compound, the compound represented by the following formula is mentioned, for example.

[Formula 14]

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent saturated aliphatic hydrocarbon group of 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. As R ^a4 , a single bond, a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a5 , a methyl group or an ethyl group is preferable, for example.

It is preferable that it is 3-25 mass %, and, as for the ratio of the structural unit derived from the said unsaturated carboxylic acid in this alkali-soluble resin, it is more preferable that it is 5-25 mass %. Moreover, it is preferable that it is 71-95 mass %, and, as for the ratio of the structural unit derived from the said epoxy-group-containing unsaturated compound, it is more preferable that it is 75-90 mass %. The ratio of the constitutional units derived from the alicyclic group-containing unsaturated compound is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass. By setting it as the said range, the adhesiveness with respect to the board|substrate of the photosensitive resin composition and the intensity|strength after hardening of the photosensitive resin composition can be improved, making alkali solubility of resin obtained suitable.

It is preferable that it is 1000-40000, and, as for the mass average molecular weight of alkali-soluble resin, it is more preferable that it is 2000-30000. By setting it as the said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

It is preferable that it is 5-80 mass % with respect to solid content of the photosensitive resin composition of a 1st aspect, and, as for content of alkali-soluble resin, it is more preferable that it is 15-50 mass %. By setting it as the said range, there exists a tendency for easy balance of developability.

As a photopolymerizable monomer in the photosensitive resin composition of the 1st aspect, there exist a monofunctional monomer and a polyfunctional monomer.

Examples of monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxymethyl. Toxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Late, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropylphthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth) Acrylates, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) acrylates, half (meth)acrylates of phthalic acid derivatives, and the like. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, as the polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di (meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin Di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acrylate Acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene Glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycy diletherpoly(meth)acrylate, urethane(meth)acrylate (i.e., tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl(meth)acrylate, methylenebis( polyfunctional monomers such as meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide; triacryl formal; and the like. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that it is 1-30 mass % with respect to solid content of the photosensitive resin composition of a 1st aspect, and, as for content of a photopolymerizable monomer, it is more preferable that it is 5-20 mass %. By setting it as the said range, it tends to be easy to balance sensitivity, developability, and resolution.

It does not specifically limit as a photoinitiator in the photosensitive resin composition of 1st aspect, A conventionally well-known photoinitiator can be used.

As the photopolymerization initiator, specifically, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl )-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1 -[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzoyl Methyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthone Santhene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3- Diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chloro Phenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl Midazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Michler's ketone), 4,4' -bisdiethylaminobenzophenone (i.e., ethylmichler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoinmethyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytri Azine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran -2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) )-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3 ,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloro) Methyl) -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, it is particularly preferable from the viewpoint of sensitivity to use an oxime-based photopolymerization initiator. Moreover, you may use the oxime ester compound mentioned later preferably. These photoinitiators can be used individually or in combination of 2 or more types.

As a preferable oxime ester compound, the compound represented by the following formula (d11) is mentioned.

[Formula 15]

In the formula (d11), R ^D13 represents an alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted carbazolyl group. 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 linear or branched. In this case, 1-8 are preferable and, as for the number of carbon atoms of an alkyl group, 1-5 are more preferable.

When R ^D13 is a phenyl group which may have a substituent, the type of substituent is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent that the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a phenoxy group which may have a substituent. Group, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthyl which may have a substituent Toxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, amino group , amino group, morpholin-1-yl group, and piperazin-1-yl group substituted with 1 or 2 organic groups, halogen, nitro group, cyano group, and the like. When R ^D13 is a phenyl group which may have a substituent and the phenyl group has a plurality of substituents, the 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 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1 do. In addition, the alkyl group may be a straight chain or a branched chain. Specific examples in the case where the substituent of the phenyl group is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isono A yl group, n-decyl group, and isodecyl group etc. are mentioned. Moreover, the alkyl group may contain the ether bond (-O-) in a carbon chain. In this case, as a substituent which a phenyl group has, an alkoxyalkyl group and an alkoxyalkoxyalkyl group are mentioned, for example. When the substituent of the phenyl group is an alkoxyalkyl group, groups represented by -R ^D16 -OR ^D17 are preferable. R ^D16 is an alkylene group having 1 to 10 carbon atoms, which may be a linear or branched chain. R ^D17 is an alkyl group having 1 to 10 carbon atoms, which may be a linear or branched chain. The number of carbon atoms in R ^D16 is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3. The number of carbon atoms in R ^D17 is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

As for the number of carbon atoms, when the substituent which a phenyl group has is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. In addition, the alkoxy group may be a straight chain or a branched chain. Specific examples in case the substituent of the phenyl group is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert- Butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec -Octioxyl group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, 2-methoxy-1-methylethoxy group, methoxyethoxyethoxy group, and ethoxyethoxy group. A oxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group etc. are mentioned.

As for the number of carbon atoms, when the substituent which a phenyl group has is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. Specific examples in case the substituent of the phenyl group 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 in case the substituent of the phenyl group is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group. .

As for the number of carbon atoms, when the substituent which a phenyl group has is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-20 are preferable and 2-7 are more preferable. Specific examples of the case where the substituent of the phenyl group is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-docanoyl group, n-tridecanoyl group, n-tetradecanoyl group , an n-pentadecanoyl group, and an n-hexadecanoyl group. Specific examples in the case where the substituent of the phenyl group is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group yloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group; and the like.

As for the number of carbon atoms, when the substituent which a phenyl group has is an alkoxycarbonyl group, 2-20 are preferable and 2-7 are more preferable. Specific examples when the substituent of the phenyl group is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, and sec-butyloxycarbonyl group. , tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyl oxycarbonyl group, sec-octioxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

As for the number of carbon atoms, when the substituent which a phenyl group has is a phenylalkyl group, 7-20 are preferable and 7-10 are more preferable. Moreover, as for the number of carbon atoms, when the substituent which a phenyl group has is a naphthylalkyl group, 11-20 are preferable and 11-14 are more preferable. As a specific example in case the substituent which a phenyl group has is a phenylalkyl group, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group are mentioned. Specific examples in the case where the substituent of the phenyl group is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. can 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 naphthyl group.

When the substituent of the phenyl group is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocycle formed by condensation of such monocyclic rings or a benzene ring. it's a reel When the heterocyclyl group is a condensed ring, the number of rings is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzooxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline; and the like. When the substituent which the phenyl group has is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When the substituent of the phenyl group is an amino group substituted with an organic group of 1 or 2, preferred examples of the organic group include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a cycloalkyl group of 2 to 20 carbon atoms. A saturated aliphatic acyl group, a saturated aliphatic acyloxy group of 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group of 7 to 20 carbon atoms which may have a substituent, a substituent The naphthyl group which may have, the naphthoyl group which may have a substituent, the C11-C20 naphthyl alkyl group which may have a substituent, the heterocyclyl group, etc. are mentioned. Specific examples of these preferred organic groups include the same as those described above for the substituents of the phenyl group. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, and di-n -Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n -butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group, and N-acetyl-N-acetyloxyamino group.

Examples of the substituent included in the substituent of the phenyl group when the phenyl group, naphthyl group, and heterocyclyl group further have a substituent include an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group of 2 to 7 carbon atoms, an alkoxycarbonyl group of 2 to 7 carbon atoms, a saturated aliphatic acyloxy group of 2 to 7 carbon atoms, an alkyl group of 1 to 6 carbon atoms, and a carbon atom number dialkylamino groups having 1 to 6 alkyl groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups; and the like. When the phenyl group, naphthyl group, and heterocyclyl group included in the substituents of the phenyl group further have substituents, the number of the substituents is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. do. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group have a plurality of substituents, the plurality of substituents may be the same or different.

In the above, the substituent in case R ^D13 is a phenyl group which may have a substituent has been described, but among these substituents, an alkyl group or an alkoxyalkyl group is preferable.

When R ^D13 is a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituent are not particularly limited as long as the object of the present invention is not impaired. When R ^D13 is a phenyl group which may have a substituent, it is preferable that the phenyl group which may have a substituent is an o-tolyl group which may have a substituent from the viewpoint of excellent base generation efficiency.

When R ^D13 is a carbazolyl group which may have a substituent, the type of substituent is not particularly limited as long as the object of the present invention is not impaired. Examples of preferable substituents that the carbazolyl group may have on the carbon atom include an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a 3 carbon atom group. cycloalkoxy group of 10 to 10, saturated aliphatic acyl group of 2 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, saturated aliphatic acyloxy group of 2 to 20 carbon atoms, phenyl group which may have a substituent, substituent A phenoxy group which may have a , a phenylthio group which may have a substituent, a phenylcarbonyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, A phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthoyl group which may have a substituent, Naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, heterocyclyl group which may have a substituent, hetero which may have a substituent a cyclylcarbonyl group, an amino group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group; and the like.

When R ^D13 is a carbazolyl group which may have a substituent, examples of preferable substituents which the carbazolyl group may have on the nitrogen atom include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, A saturated aliphatic acyl group of 2 to 20 carbon atoms, an alkoxycarbonyl group of 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, even if it has a substituent phenylalkyl group of 7 to 20 carbon atoms, naphthyl group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyl group which may have a substituent of 11 to 20 carbon atoms A tylalkyl group, the heterocyclyl group which may have a substituent, and the heterocyclyl carbonyl group which may have a substituent, etc. are mentioned. Among these substituents, an alkyl group of 1 to 20 carbon atoms is preferable, an alkyl group of 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group which may have a substituent, and a substituent Regarding the naphthylalkyl group which may have, the heterocyclyl group which may have a substituent, and the amino group substituted with 1 or 2 organic groups, examples of substituents possessed by the phenyl group when R ^D13 is a phenyl group which may have a substituent, and same.

In R ^D13 , examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the carbazolyl group further have a substituent include an alkyl group of 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group of 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; Benzoyl group; naphthoyl group; a benzoyl group substituted with 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; Monoalkylamino group which has a C1-C6 alkyl group; dialkylamino group having an alkyl group of 1 to 6 carbon atoms; morpholine-1-yl group; piperazine-1-diyl; halogen; nitro group; A cyano group is mentioned. When the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the carbazolyl group further have a substituent, the number of the substituent is not limited to the range not impairing the object of the present invention, but 1 to 4 desirable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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 linear or branched. In this case, 1-8 are preferable and, as for the number of carbon atoms of an alkyl group, 1-5 are more preferable.

In R ^D14 , the substituent of the alkyl group, phenyl group or carbazolyl group is not particularly limited as long as the object of the present invention is not impaired.

Examples of preferable substituents that the alkyl group may have on the carbon atom include an alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a cycloalkoxy group of 3 to 10 carbon atoms, and a 2 carbon atom group. saturated aliphatic acyl group of 20 to 20, alkoxycarbonyl group of 2 to 20 carbon atoms, saturated aliphatic acyloxy group of 2 to 20 carbon atoms, phenyl group which may have a substituent, phenoxy group which may have a substituent, even if it has a substituent A phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, even if it has a substituent naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, carbon atom number which may have a substituent 11 to 20 naphthylalkyl groups, heterocyclyl groups which may have substituents, heterocyclylcarbonyl groups which may have substituents, amino groups, amino groups substituted with 1 or 2 organic groups, morpholin-1-yl groups, and piperazine-1 - Diary group, halogen group, nitro group, and cyano group, etc. are mentioned.

Examples of preferable substituents that the phenyl group and the carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms in addition to the groups exemplified above as the preferable substituents the alkyl group may have on the carbon atom. can

As for the specific examples of the substituent that the alkyl group, phenyl group or carbazolyl group may have, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, which may have a substituent Regarding a phenylalkyl group, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted with 1 or 2 organic groups, the phenyl group in case R ^D13 is a phenyl group which may have a substituent It is the same as the example of the substituent having.

In R ^D14 , examples of substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the alkyl group, phenyl group, or carbazolyl group further have a substituent include an alkyl group of 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group of 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; Benzoyl group; naphthoyl group; a benzoyl group substituted with 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; Monoalkylamino group which has a C1-C6 alkyl group; dialkylamino group having an alkyl group of 1 to 6 carbon atoms; morpholine-1-yl group; piperazine-1-diyl; halogen; nitro group; A cyano group is mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the alkyl group or the phenyl group further have a substituent, the number of the substituent is not limited within the range not impairing the object of the present invention, but 1 to 4 desirable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

From the point of the base generation efficiency of the compound represented by formula (d11), as R ^D14 , the following formula (d12):

[Formula 16]

A group represented by , and the following formula (d13):

[Formula 17]

The group represented by is preferable.

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

R ^D18 in the formula (d12) can be selected from various organic groups within a range not impairing the object of the present invention. Preferable examples of R ^D18 include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a saturated aliphatic acyl group of 2 to 20 carbon atoms, an alkoxycarbonyl group of 2 to 20 carbon atoms, and a substituent. The phenyl group which may have, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, the naphthyl group which may have a substituent, the naphthyl group which may have a substituent, which may have a substituent a naphthoyl group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent, etc. can be heard

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

R ^D19 in the formula (d12) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of groups suitable for R ^D19 include an alkyl group of 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclyl group. As R ^D19 , among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are more preferable, and a 2-methylphenyl group and a naphthyl group are particularly preferable.

As a substituent in case the phenyl group, naphthyl group, and heterocyclyl group contained in R ^D18 or R ^D19 further have a substituent, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, carbon A monoalkylamino group having a saturated aliphatic acyl group of 2 to 7 atoms, an alkoxycarbonyl group of 2 to 7 carbon atoms, a saturated aliphatic acyloxy group of 2 to 7 carbon atoms, an alkyl group of 1 to 6 carbon atoms, a carbon atom Dialkylamino group having an alkyl group of 1 to 6, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^D18 or R ^D19 further have a substituent, the number of the substituent is not limited to the range not impairing the object of the present invention, but 1 to 4 desirable. When the phenyl group, naphthyl group, and heterocyclyl 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 can be selected from various organic groups within a range not impairing the object of the present invention. Preferred examples in the case where R ^D20 in the formula (d13) is an organic group include an alkyl group of 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group of 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; Benzoyl group; naphthoyl group; a benzoyl group substituted with 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; Monoalkylamino group which has a C1-C6 alkyl group; dialkylamino group having an alkyl group of 1 to 6 carbon atoms; morpholine-1-yl group; piperazine-1-diyl; halogen; nitro group; cyano group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; A 4-(phenyl)phenylcarbonyl group is mentioned.

Among R ^D20 , benzoyl group; naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, and it is a benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; A 4-(phenyl)phenylcarbonyl group is more preferred.

In formula (d13), y2 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When y2 is 1, the position at which R ^D20 is bonded is preferably para-position with respect to the bond at which the phenyl group to which R ^D20 is bonded is bonded to a sulfur atom.

R ^D15 is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, or a phenyl group which may have a substituent. In the case of a phenyl group which may have a substituent, the substituent which the phenyl group may have is the same as that in the case where 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 preferable, and a methyl group or a phenyl group is more preferable.

When x1 is 0, the oxime ester compound represented by the said formula (d11) is compoundable by the method demonstrated below, for example. First, the ketone compound represented by R ^D14 -CO-R ^D13 is oximated with hydroxylamine to obtain an oxime compound represented by R ^D14 -(C=N-OH)-R ^D13 . Next, the obtained oxime compound is acylated with an acid halide represented by R ^D15 -CO-Hal (Hal represents halogen) or an acid anhydride represented by (R ^D15 CO) ₂ O, and x1 is 0 in the above formula An oxime ester compound represented by (d11) is obtained.

Moreover, when x1 is 1, the oxime ester compound represented by the said formula (d11) is compoundable by the method demonstrated below, for example. First, the ketone compound represented by R ^D14 -CO-CH ₂ -R ^D13 is reacted with a nitrite ester in the presence of hydrochloric acid to obtain an oxime compound represented by R ^D14 -CO-(C=N-OH)-R ^D13 . Next, the obtained oxime compound is acylated with an acid halide represented by R ^D15 -CO-Hal (Hal represents halogen) or an acid anhydride represented by (R ^D15 CO) ₂ O, and x1 is 1 in the above formula An oxime ester compound represented by (d11) is obtained.

As a compound represented by the said formula (d11), the compound represented by the following formula (d14) is mentioned.

[Formula 18]

In the 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 amino group, a halogen, a nitro group, and a cyano group, x2 is an integer of 0 to 4, and R ^D22 is a hydrogen atom or 1 to 6 carbon atoms is an alkyl group of

In the formula (d14), R ^D21 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups when it is an organic group. Preferable examples of R ^D21 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, and a substituent. A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a substituent A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, an amino group, 1 or 2 amino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group substituted with an organic group of . When x2 is an integer of 2 to 4, R ^D21 may be the same or different. Moreover, the number of carbon atoms of the substituent which a substituent further has is not included in the number of carbon atoms of a substituent.

When R ^D21 is an alkyl group, it preferably has 1 to 20 carbon atoms and more preferably has 1 to 6 carbon atoms. Moreover, when R ^D21 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^D21 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso pentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. Moreover, 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^D21 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^D21 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples in case R ^D21 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group. period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Thioxyl group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R ^D21 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and A methoxypropyloxy group etc. are mentioned.

When R ^D21 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples in case 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 in case R ^D21 is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

When R ^D21 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples of when R ^D21 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexa Noyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, An n-pentadecanoyl group, an n-hexadecanoyl group, etc. are mentioned. Specific examples in case R ^D21 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoloxy group. Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^D21 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples in case R ^D21 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert -Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group , sec-octioxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^D21 is a phenylalkyl group, it preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. Moreover, when R ^D21 is a naphthylalkyl group, 11 to 20 carbon atoms are preferable, and 11 to 14 carbon atoms are more preferable. Specific examples in case 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 in case R ^D21 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. . When R ^D21 is a phenylalkyl group or a naphthylalkyl group, R ^D21 may further have a substituent on the phenyl group or naphthyl group.

When R ^D21 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclyl group formed by condensation of such monocyclic rings or a benzene ring. . When the heterocyclyl group is a condensed ring, the number of rings is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzooxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline; and the like. When R ^D21 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^D21 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic groups are alkyl groups of 1 to 20 carbon atoms, cycloalkyl groups of 3 to 10 carbon atoms, and saturated aliphatic groups of 2 to 20 carbon atoms. an acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, C11-C20 naphthylalkyl group which may have a substituent, heterocyclyl group, etc. are mentioned. Specific examples of these preferable organic groups are the same as for R ^D21 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. can be heard

Examples of substituents in R ^D21 when the phenyl group, naphthyl group, and heterocyclyl group further have a substituent include an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and a 2 carbon atom group. A monoalkylamino group having a saturated aliphatic acyl group of 7 to 7 atoms, an alkoxycarbonyl group of 2 to 7 carbon atoms, a saturated aliphatic acyloxy group of 2 to 7 carbon atoms, an alkyl group of 1 to 6 carbon atoms, and an alkyl group of 1 to 6 carbon atoms. dialkylamino groups having 6 alkyl groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups; and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^D21 further have a substituent, the number of the substituent is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^D21 have a plurality of substituents, the plurality of substituents may be the same or different.

In R ^D21 , from the viewpoint of chemical stability, little steric hindrance, and easy synthesis of oxime ester compounds, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and a carbon atom A group selected from the group consisting of a saturated aliphatic acyl group of 2 to 7 atoms is preferred, an alkyl group of 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

The position at which R ^D21 is bonded to the phenyl group is, relative to the phenyl group to which R ^D21 is bonded, when the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is the 1 position and the position of the methyl group is the 2 position, 4 The position or the 5th position is preferred, and the 5th position is more preferred. Moreover, x2 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

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

The specific example of a compound especially preferable as an oxime ester compound is shown below.

[Formula 19]

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

[Formula 20]

(R ^D23 is a hydrogen atom, a nitro group or a monovalent organic group, R ^D24 and R ^D25 are each a chain-like alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^D24 and R ^D25 may 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 a substituent which may have aryl group, x4 is an integer from 0 to 4, and x3 is 0 or 1.)

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

When R ^D23 is an organic group, R ^D23 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferable examples when R ^D23 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a phenoxy group which may have a substituent. Group, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthyl which may have a substituent Toxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, substituent The heterocyclylcarbonyl group which may have, the amino group substituted with 1 or 2 organic groups, the morpholin-1-yl group, the piperazin-1-yl group, etc. are mentioned.

As for the number of carbon atoms of an alkyl group, when R ^D23 is an alkyl group, 1-20 are preferable and 1-6 are more preferable. Moreover, when R ^D23 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when 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, n-pentyl group, iso pentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. Moreover, 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

As for the number of carbon atoms in an alkoxy group, when R ^D23 is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. Moreover, when R ^D23 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples in case R ^D23 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group. period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Thioxyl group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R ^D23 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and A methoxypropyloxy group etc. are mentioned.

As for the carbon atom number of a cycloalkyl group or a cycloalkoxy group, when R ^D23 is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group etc. are mentioned as a specific example in case R ^D23 is a cycloalkyl group. Specific examples in case R ^D23 is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

As for the carbon atom number of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, when R ^D23 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-21 are preferable and 2-7 are more preferable. Specific examples of when R ^D23 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexa Noyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, An n-pentadecanoyl group, an n-hexadecanoyl group, etc. are mentioned. Specific examples in case R ^D23 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoloxy group. Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

As for the carbon atom number of an alkoxycarbonyl group, when R ^D23 is an alkoxycarbonyl group, 2-20 are preferable and 2-7 are more preferable. Specific examples in case R ^D23 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert -Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group , sec-octioxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

As for the carbon atom number of a phenylalkyl group, when R ^D23 is a phenylalkyl group, 7-20 are preferable and 7-10 are more preferable. Moreover, when R ^D23 is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. Specific examples in case 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 in the case where R ^D23 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. . When R ^D23 is a phenylalkyl group or a naphthylalkyl group, R ^D23 may further have a substituent on the phenyl group or naphthyl group.

When R ^D23 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more of N, S, and O, or a heterocyclyl group formed by condensation of such monocyclic rings or a benzene ring. . When the heterocyclyl group is a condensed ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzooxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, and phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ^D23 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^D23 is a heterocyclylcarbonyl group, the heterocyclyl groups contained in the heterocyclylcarbonyl group are the same as those in the case where R ^D23 is a heterocyclyl group.

When R ^D23 is an amino group substituted with an organic group of 1 or 2, preferred examples of the organic group include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a saturated aliphatic group of 2 to 21 carbon atoms. an acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, C11-C20 naphthylalkyl group which may have a substituent, heterocyclyl group, etc. are mentioned. Specific examples of these preferable organic groups are the same as those of R ^D23 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, and di-n -Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n -butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group etc. can be mentioned.

Examples of substituents in R ^D23 in which the phenyl group, naphthyl group, and heterocyclyl group further have a substituent include an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and a 2 carbon atom group. A monoalkylamino group having a saturated aliphatic acyl group of 7 to 7 atoms, an alkoxycarbonyl group of 2 to 7 carbon atoms, a saturated aliphatic acyloxy group of 2 to 7 carbon atoms, an alkyl group of 1 to 6 carbon atoms, and an alkyl group of 1 to 6 carbon atoms. dialkylamino groups having 6 alkyl groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups; and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^D23 further have a substituent, the number of the substituent is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^D23 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, a nitro group or a group represented by R ^D28 -CO- as R ^D23 is preferable because the sensitivity tends to be improved. R ^D28 is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of a group suitable for 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 heterocyclyl group which may have a substituent. As R ^D28 , among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferred.

In addition, when R ^D23 is a hydrogen atom, transparency tends to be good, which is preferable when forming a cured film requiring transparency. Transparency tends to be better when R ^D23 is a hydrogen atom and R ^D26 is a group represented by the formula (R4-2) described later.

In formula (d15), R ^D24 and R ^D25 are each a chain-like 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 combine with each other to form a ring. Among these groups, chain-like alkyl groups which may have substituents are preferred as R ^D24 and R ^D25 . When R ^D24 and R ^D25 are chain-like alkyl groups which may have substituents, the chain-like alkyl groups may be straight-chain alkyl groups or branched-chain alkyl groups.

When R ^D24 and R ^D25 are chain-like alkyl groups having no substituent, the number of carbon atoms in the chain-like alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. Specific examples when R ^D24 and R ^D25 are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group , isononyl group, n-decyl group, and isodecyl group. Moreover, 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

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

Substituents that the alkyl group may have are not particularly limited as long as the object of the present invention is not impaired. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group are mentioned. Specific examples of the cycloalkyl group are the same as the preferred examples in case R ^D23 is a cycloalkyl group. A phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group etc. are mentioned as a specific example of an aromatic hydrocarbon group. Specific examples of the heterocyclyl group are the same as those in the case where R ^D23 is a heterocyclyl group. When R ^D23 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. 1-10 are preferable and, as for the number of carbon atoms of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

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

When R ^D24 and R ^D25 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. As a cyclic organic group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group are mentioned. When R ^D24 and R ^D25 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as those when R ^D24 and R ^D25 are chain alkyl groups.

When R ^D24 and R ^D25 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. . When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of rings of the benzene rings contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, 1 is particularly preferred. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl 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 in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20 and 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 norbornyl group, an isobornyl group, a tricyclononyl group, and a tricyclo. A decyl group, a tetracyclododecyl group, and an adamantyl group etc. are mentioned.

When R ^D24 and R ^D25 represent a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclic ring formed by condensation of such monocyclic rings or a benzene ring. It is a cyclyl group. When the heterocyclyl group is a condensed ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzooxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, and phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

R ^D24 and R ^D25 may combine with each other to form a ring. The group consisting of a ring formed by R ^D24 and R ^D25 is preferably a cycloalkylidene group. When R ^D24 and R ^D25 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, more preferably a 5-membered ring.

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

Examples of preferable groups among R ^D24 and R ^D25 described above include groups 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.

1-10 are preferable and, as for carbon atoms of the linear alkylene group of A ^D1 , 1-6 are more preferable. When A ^D2 is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. 1-10 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. When A ^D2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ^D2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, chlorine atom, bromine atom or iodine atom, and more preferably a fluorine atom, chlorine atom or bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ^D2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^D24 and R ^D25 have as substituents. When A ^D2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R ^D24 and R ^D25 have as substituents.

Specific preferable examples of R ^D24 and R ^D25 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phen alkoxyalkyl groups such as ethyl group, 6-ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group -cyanoalkyl groups such as n-heptyl group and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and phenylalkyl groups such as 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-phen cycloalkylalkyl groups such as a ethyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and a 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl -n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and 8 -Alkoxycarbonylalkyl groups such as an ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5, Halogenated alkyl groups, such as a 5-heptafluoro-n-pentyl group, are mentioned.

Preferred groups among the above as R ^D24 and R ^D25 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group , 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro -n-pentyl group.

Examples of preferred organic groups for R ^D26 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a substituent as in R ^D23 . The phenoxy group which may have, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, the substituent The naphthoxy group which may have a substituent, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, the hetero which may have a substituent A cyclyl group, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ^D23 . Moreover, as R ^D26 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on an aromatic ring, and a phenylthioalkyl group which may have a substituent on an aromatic ring are preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ^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, and a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, particularly preferably an alkyl group of 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and a 2-methylphenyl group is more preferable. 5-10 are preferable, as for the carbon atom number of the cycloalkyl group contained in a cycloalkylalkyl group, 5-8 are more preferable, and 5 or 6 are especially preferable. 1-8 are preferable, as for the number of carbon atoms of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 are especially preferable. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferable.

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

When A ^D3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. As for the number of carbon atoms of an alkylene group, when A ^D3 is an alkylene group, 1-10 are preferable, 1-6 are more preferable, and 1-4 are especially preferable.

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

-A ^D3 -CO-OA Specific preferred examples of the group represented by ^D4 include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyl Oxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n -Propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxy carbonyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, and 3-phenoxycarbonyl-n-propyl group; can

In the above, R ^D26 has been described, but as R ^D26 , a group represented by the following formula (R4-1) or (R4-2) is preferable.

[Formula 21]

(In formulas (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 adjacent to each other on the benzene ring. In this case, R ^D29 and R ^D30 may combine with each other to form a ring, z2 is an integer of 1 to 8, z3 is an integer of 1 to 5, z4 is an integer of 0 to (r + 3), and R ⁹ is an organic group.)

Examples of the organic group for R ^D29 and R ^D30 in the formula (R4-1) are the same as for R ^D23 . As R ^D29 , an alkyl group or a phenyl group is preferable. As for the number of carbon atoms, when R ^<29> is an alkyl group, 1-10 are preferable, 1-5 are more preferable, 1-3 are especially preferable, and 1 is the most preferable. In short, it is most preferable that R ^D29 is a methyl group. When R ^D29 and R ^D30 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. As the group represented by formula (R4-1), preferred examples of the group in which R ^D29 and R ^D30 form a ring include a naphthalen-1-yl group and a 1,2,3,4-tetrahydronaphthalen-5-yl group. etc. can be mentioned. In the formula (R4-1), z1 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

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

In the formula (R4-2), z3 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the formula (R4-2), z4 is 0 to (z3 + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0. In the 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 formula (d15), R ^D27 is a hydrogen atom, an alkyl group of 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As a substituent which may have when v is an alkyl group, a phenyl group, a naphthyl group, etc. are illustrated preferably. Moreover, as a substituent which may have when R ^D23 is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In 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, a naphthyl group, etc. are exemplified preferably, and among these , a methyl group or a phenyl group is more preferred.

The manufacturing method of the compound represented by formula (d15) is not specifically limited. The compound represented by the formula (d15) preferably includes a step of converting an oxime group (=N-OH) contained in a compound represented by the following formula (d16) into an oxime ester group represented by =NO-COR ^D27 is manufactured by R ^D27 is the same as R ^D27 in formula (d15).

[Formula 22]

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

For this reason, the compound represented by the formula (d16) is useful as an intermediate for synthesis of the compound represented by the formula (d15).

The method of converting an oxime group (=N-OH) into an oxime ester group represented by =NO-COR ^D27 is not particularly limited. Typically, a method of reacting an acylating agent that imparts an acyl group represented by -COR ^D27 to the hydroxyl group in the oxime group is exemplified. Examples of the acylating agent include acid anhydrides represented by (R ^D27 CO) ₂ O and acid halides represented by R ^D27 COHal (Hal is a halogen atom).

When x3 is 0, the compound represented by formula (d15) is compoundable according to scheme 1 below, for example. In Scheme 1, a fluorene 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 fluorene derivative represented by formula (d1-1) is a fluorene derivative in which the 9th position is substituted with R ^D24 and R ^D25 , and the substituent R ^D23 is substituted by a known method. can be obtained by introducing The fluorene derivative in which the 9-position is substituted with R ^D24 and R ^D25 , for example, when R ^D24 and R ^D25 are alkyl groups, as described in Japanese Patent Laid-Open No. 06-234668, in the presence of an alkali metal hydroxide, It can be obtained by reacting fluorene with an alkylating agent in an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene to carry out an alkylation reaction, 9-alkyl substituted fluorenes can be obtained.

An acyl group represented by -CO-R ^D26 is introduced into the fluorene derivative represented by the formula (d1-1) by a Friedel Crafts acylation reaction to obtain a fluorene derivative represented by the formula (d1-3). The acylating agent for introducing an acyl group represented by -CO-R ^D26 may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by formula (d1-2) is preferable. In formula (d1-2), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by appropriately changing the conditions of the Friedel Crafts reaction or by performing protection and deprotection at positions other than the position to be acylated.

Subsequently, the group represented by -CO-R ^D26 in the obtained fluorene derivative represented by formula (d1-3) is converted into a group represented by -C(=N-OH)-R ^D26 to obtain an oxime represented by formula (d1-4) get a compound Although the method of converting the group represented by -CO-R ^D26 into the group represented by -C(=N-OH)-R ^D26 is not particularly limited, oximation by hydroxylamine is preferred. An oxime compound of formula (d1-4), an acid anhydride ((R ^D27 CO) ₂ O) represented by the following formula (d1-5), or an acid halide (R ^D27 COHal, Hal represented by the following formula (d1-6) silver halogen atom) can be reacted to obtain a compound represented by the following formula (d1-7).

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 in formula (d15).

In Scheme 1, R ^D26 contained in each of the formulas (d1-2), (d1-3), and (d1-4) may be the same or different. In short, R ^D26 in formulas (d1-2), formulas (d1-3), and formulas (d1-4) may be chemically modified in the synthesis process represented by Scheme 1. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical formulas that R ^D26 can accept are not limited to these.

<Scheme 1>

[Formula 23]

When x3 is 1, the compound represented by formula (d15) is compoundable according to scheme 2 below, for example. In Scheme 2, a fluorene derivative represented by the following formula (d1-7) is used as a raw material. The fluorene derivative represented by the formula (d2-1) is a compound represented by the formula (d1-1) by the same method as in Scheme 1, by Friedel Crafts reaction, an acyl group represented by -CO-CH ₂ -R ^D26 is formed. obtained by introducing As the acylating agent, a carboxylic acid halide represented by formula (d1-8): Hal-CO-CH ₂ -R ^D26 is preferable. Subsequently, the methylene group present between R ^D26 and the carbonyl group in the compound represented by the formula (d1-7) is oximated to obtain a ketoxime compound represented by the following formula (d2-3). The method of oximating the methylene group is not particularly limited, but a method of reacting a nitrite ester represented by the following formula (d2-2) (RONO, R is an alkyl group of 1 to 6 carbon atoms) in the presence of hydrochloric acid is preferable. Next, a ketoxime compound represented by the following formula (d2-3), an acid anhydride ((R ^D27 CO) ₂ O) represented by the following formula (d2-4), or an acid halide represented by the following formula (d2-5) R ^D27 COHal, Hal is a halogen atom) to react 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 is the same as in formula (d15).

Moreover, in scheme 2, R ^D26 contained in each of formula (d1-8), formula (d2-1), and formula (d2-3) may be the same or different. In short, R ^D26 in formulas (d1-8), formulas (d2-1), and formulas (d2-3) may be chemically modified in the synthesis process represented by scheme 2. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical formulas that R ^D26 can accept are not limited to these.

<Scheme 2>

[Formula 24]

As a preferable specific example of the compound represented by formula (d15), the following oxime ester compounds are mentioned.

[Formula 25]

[Formula 26]

It is preferable that content of a photoinitiator is 0.5-20 mass parts with respect to 100 mass parts of solid content of the photosensitive resin composition of a 1st aspect. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained, and also the ability to form a coating film can be improved and curing failure can be suppressed.

As described above, the photosensitive resin composition of the first aspect contains the compound represented by the formula (1). This compound has good solubility in organic solvents, and when incorporated in a photosensitive resin composition, good micropatterning properties can be obtained.

It is preferable that it is 0.5-95 mass parts with respect to 100 mass parts of the said photoinitiator, and, as for content of the compound represented by said formula (1), it is more preferable that it is 1-50 mass parts. By setting it as the said range, favorable micropatterning characteristic can be obtained, obtaining favorable developability.

The photosensitive resin composition of the first aspect may further contain a coloring agent. By containing a coloring agent, it is preferably used as a color filter formation use of a liquid crystal display, for example. Moreover, the photosensitive resin composition of the 1st aspect is suitably used as a black-matrix formation use in a color filter, for example by containing a light-shielding agent as a coloring agent.

Although the colorant is not particularly limited, for example, a compound classified as a pigment in the color index (C.I.; published by The Society of Dyers and Colourists), specifically the following color index (C.I.) It is preferable to use numbered ones.

C. I. Pigment Yellow 1 (hereinafter "C. I. Pigment Yellow" is the same, only numbers are written), 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;

C. I. Pigment Orange 1 (hereinafter "C. I. Pigment Orange" is the same, only numbers are written), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;

C. I. Pigment Violet 1 (hereinafter "C. I. Pigment Violet" is the same and only numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C. I. Pigment Red 1 (hereinafter "C. I. Pigment Red" is the same, only numbers are written), 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;

C. I. Pigment Blue 1 (hereinafter "C. I. Pigment Blue" is the same, only numbers are described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66;

C. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 37;

C. I. Pigment Brown 23, C. I. Pigment Brown 25, C. I. Pigment Brown 26, C. I. Pigment Brown 28;

C. I. Pigment Black 1, C. I. Pigment Black 7.

Moreover, when using a colorant as a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. Black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, and the like, to organic and inorganic substances. Regardless, various pigments can be mentioned. Among these, it is preferable to use carbon black having high light-shielding properties.

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

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a black matrix of a liquid crystal display, there is little current leakage, and a highly reliable, low-power display can be produced.

In addition, in order to adjust the color tone of carbon black, you may add the said organic pigment suitably as an auxiliary pigment.

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

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

What is necessary is just to determine content of a coloring agent suitably according to the use of the photosensitive resin composition of the 1st aspect, but as an example, 5-70 mass parts is preferable with respect to 100 mass parts of solids of the photosensitive resin composition of the 1st aspect, 25-60 mass parts more preferable

In particular, when forming a black matrix using the photosensitive resin composition of the 1st aspect, adjusting the quantity of the light-shielding agent in the photosensitive resin composition so that the OD value per 1 micrometer of film thickness of a black matrix may become 4 or more desirable. If the OD value per 1 micrometer of film thickness in a black matrix is 4 or more, when using for the black matrix of a liquid crystal display, sufficient display contrast can be obtained.

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

Examples of the organic solvent in the photosensitive resin composition of the first aspect include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di (poly)alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoic acid; Aromatic hydrocarbons, such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These organic solvents can 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, 3 - Methoxybutyl acetate exhibits excellent solubility with respect to the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the compound represented by the formula (1), and improves the dispersibility of the colorant. It is preferable because it can be used, and it is particularly preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate.

As for content of the organic solvent, the solid content concentration of the photosensitive resin composition of the 1st aspect is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass.

The photosensitive resin composition of the 1st aspect may contain various additives as needed. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion accelerator, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant. In addition, as optional additives, 1-(N,N-di(2-ethylhexyl)amino)methyl-1H-benzotriazole, 1-(N,N-di(2-ethylhexyl)amino)methyl-1H- Benzotriazole derivatives such as methylbenzotriazole, carboxybenzotriazole, benzotriazole, methylbenzotriazole, dihydroxypropylbenzotriazole, and bisaminomethylbenzotriazole may be used alone or in combination of two or more. do.

What is necessary is just to adjust the addition amount of various additives suitably in the range of 0.001 mass % - 10 mass % with respect to the whole composition, Preferably it is 0.1-5 mass %.

In addition, when alkali-soluble resin has a carboxyl group, even if it contains alkali-soluble resin, the compound represented by said Formula (1), and an organic solvent, and does not contain a photopolymerizable monomer and a photoinitiator, as a photosensitive resin composition function That is, when a base is generated from the compound represented by the formula (1) by electromagnetic wave irradiation or heating, the base is used as a catalyst to dehydrate and condense the alkali-soluble resin. This lowers the solubility in the developing solution.

In this case, since generation of the base from the compound represented by the said formula (1) is accelerated|stimulated when a photoinitiator is further contained, it is preferable. That is, when radicals are generated from the photopolymerization initiator by electromagnetic wave irradiation, the compound represented by the formula (1) is attacked by the radicals, and generation of a base is promoted. In addition, when the base generated from the compound represented by the above formula (1) replenishes the radical, the equilibrium of the base generating reaction is shifted, and a base is further generated. In addition, the base generated from the compound represented by the above formula (1) reacts with the compound after radical generation, and base generation is further promoted.

(2) The photosensitive resin composition of the second aspect

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

As alkali-soluble resin which has a phenolic hydroxyl group in the photosensitive resin composition of a 2nd aspect, polyhydroxy styrene-type resin can be used, for example.

Polyhydroxystyrene-based resin has at least a structural unit derived from hydroxystyrene.

Here, "hydroxystyrene" refers to hydroxystyrene, and those in which the hydrogen atom bonded to the α position of hydroxystyrene is substituted with other substituents such as halogen atoms, alkyl groups, and halogenated alkyl groups, and hydroxystyrene derivatives (monomers ) as a concept that includes

"Hydroxystyrene derivatives" have at least a benzene ring and a hydroxyl group bonded thereto, and include, for example, a hydrogen atom bonded to the α position of hydroxystyrene, a halogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group, and the like. Those substituted with other substituents, and those in which an alkyl group having 1 to 5 carbon atoms is further bonded to the benzene ring to which the hydroxyl group of hydroxystyrene is bonded, and those in which 1 to 2 hydroxyl groups are further bonded to the benzene ring to which this hydroxyl group is bonded ( At this time, the total number of hydroxyl groups is 2 to 3).

A chlorine atom, a fluorine atom, a bromine atom etc. are mentioned as a halogen atom, A fluorine atom is preferable.

In addition, "the α position of hydroxystyrene" refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

A structural unit derived from this hydroxystyrene is represented by the following formula (b-1), for example.

[Formula 27]

In the 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 Represents an integer of 0 to 2.

The alkyl group of R ^b1 preferably has 1 to 5 carbon atoms. Further, linear or branched alkyl groups are preferred, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl groups. etc. can be mentioned. Among these, a methyl group is industrially preferable.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

As the halogenated alkyl group, a part or all of the hydrogen atoms of the above-mentioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Among these, those in which all of the hydrogen atoms are substituted with fluorine atoms are preferable. Further, a linear or branched fluorinated alkyl group is preferable, a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group and the like are more preferable, and a trifluoromethyl group (-CF ₃ ) is most preferred.

As R ^b1 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

Examples of the alkyl group of 1 to 5 carbon atoms for R ^b2 include the same as those for R ^b1 .

q is an integer of 0 to 2; Among these, 0 or 1 is preferable, and 0 is particularly preferable for industrial purposes.

When q is 1, the substitution position of R ^b2 may be any of an ortho position, a meta position, and a para position, and when q is 2, an arbitrary substitution position can be combined.

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

When p is 1, the substitution position of a hydroxyl group may be any of an ortho position, a meta position, and a para position, but the para position is preferable in terms of being easily available and inexpensive. In addition, when p is 2 or 3, arbitrary substitution positions can be combined.

The structural unit represented by the said formula (b-1) can be used individually or in combination of 2 or more types.

In the polyhydroxystyrene-based resin, the ratio of the structural units derived from hydroxystyrene is preferably 60 to 100 mol%, and 70 to 100 mol%, based on all the structural units constituting the polyhydroxystyrene-based resin. It is more preferable, and it is more preferable that it is 80-100 mol%. By setting it in the said range, when it is set as the photosensitive resin composition, moderate alkali solubility is obtained.

It is preferable that the polyhydroxystyrene-based resin further has a structural unit derived from styrene.

Here, the term "structural unit derived from styrene" includes a structural unit obtained by cleavage of an ethylenic double bond of styrene and a styrene derivative (however, hydroxystyrene is not included).

"Styrene derivatives" are those in which the hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and the hydrogen atom of the phenyl group of styrene is substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms. to be included, etc.

A chlorine atom, a fluorine atom, a bromine atom etc. are mentioned as a halogen atom, A fluorine atom is preferable.

In addition, "the α position of styrene" refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

A structural unit derived from this styrene is represented by the following formula (b-2), for example. In the formula, R ^b1 , R ^b2 , and q have the same meaning as in the formula (b-1).

[Formula 28]

Examples of ^Rb1 and ^Rb2 include the same ones as ^Rb1 and ^Rb2 in the above formula (b-1), respectively.

q is an integer of 0 to 2; Among these, 0 or 1 is preferable, and 0 is particularly preferable for industrial purposes.

When q is 1, the substitution position of R ^b2 may be any of an ortho position, a meta position, and a para position, and when q is 2, an arbitrary substitution position can be combined.

The structural unit represented by the said formula (b-2) can be used individually or in combination of 2 or more types.

In the polyhydroxystyrene-based resin, the ratio of the constituent units derived from styrene is preferably 40 mol% or less, more preferably 30 mol% or less, and 20 mol% or less with respect to all constituent units constituting the polyhydroxystyrene-based resin. It is more preferable that it is % or less. By setting it as the said range, while moderate alkali solubility is obtained when it is set as the photosensitive resin composition, the balance with other structural units also becomes favorable.

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

Although the mass average molecular weight of polyhydroxy styrene-type resin is not specifically limited, 1500-40000 are preferable and 2000-8000 are more preferable.

Moreover, a novolak resin can also be used as alkali-soluble resin which has a phenolic hydroxyl group. This novolac resin can be obtained by subjecting phenols and aldehydes to addition condensation in the presence of an acid catalyst.

Examples of the phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. Ilenols; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p- Alkyl phenols, such as tert- butyl phenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; alkyl polyhydric phenols such as alkyl resorcinol, alkyl catechol, and alkyl hydroquinone (one of the alkyl groups has 1 to 4 carbon atoms); [alpha]-naphthol, [beta]-naphthol, hydroxydiphenyl, bisphenol A, etc. are mentioned. These phenols can be used individually or in combination of 2 or more types.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics, such as a sensitivity, can be adjusted by adjusting the mixing ratio of both.

Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

As an acid catalyst, 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, diethylsulfuric acid, and p-toluenesulfonic acid; Metal salts, such as zinc acetate, etc. are mentioned. These acid catalysts can be used alone or in combination of two or more.

Specific examples of the novolak resin obtained in this way include phenol/formaldehyde condensed novolak resins, cresol/formaldehyde condensed novolac resins, and phenol-naphthol/formaldehyde condensed novolac resins.

The mass average molecular weight of the novolac resin is not particularly limited, but is preferably from 1000 to 30000, and more preferably from 3000 to 25000.

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

It is preferable that it is 20-80 mass % with respect to solid content of the photosensitive resin composition of a 2nd aspect, and, as for content of alkali-soluble resin which has a phenolic hydroxyl group, it is more preferable that it is 35-65 mass %. By setting it as the said range, there exists a tendency for easy balance of developability.

It does not specifically limit as an acid crosslinkable substance in the photosensitive resin composition of a 2nd aspect, A conventionally well-known acid crosslinkable substance can be used.

Specifically as the acid crosslinking material, an amino resin having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, acetoguanamine resin, benzoguanamine resin, glycoluril-formaldehyde resin, Succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin, etc. are mentioned. These acid crosslinkable materials are methylolized by reacting melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinylamide, and ethyleneurea with formalin in boiling water, or reacting with lower alcohol in addition to this. It is easily obtained by alkoxylation with For practical use, it can be obtained as melamine resins such as Nigalak MX-750, Nigalak MW-30, and Nigalak MW100LM, and urea resins such as Nigalac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). Moreover, benzoguanamine resins, such as Cymel 1123 and Cymel 1128 (made by Mitsui Cyanad Co., Ltd.), can also be obtained as a commercial item.

In addition, alkoxy such as 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, 1,4-bis (sec-butoxymethoxy) benzene A phenolic compound having a hydroxyl group or an alkoxyl group, such as a benzene compound having a practical group and 2,6-dihydroxymethyl-p-tert-butylphenol, can also be used.

These acid crosslinkable substances can be used alone or in combination of two or more.

It is preferable that it is 5-50 mass parts with respect to 100 mass parts of alkali-soluble resin which has a phenolic hydroxyl group, and, as for content of an acid crosslinkable substance, it is more preferable that it is 10-30 mass parts. By setting it as the said range, the sclerosis|hardenability of the photosensitive resin composition and patterning property become favorable.

It does not specifically limit as a photoacid generator in the photosensitive resin composition of a 2nd aspect, A conventionally well-known photoacid generator can be used.

Specific examples of the photoacid generator include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, halogen-containing triazine compounds, diazomethane-based acid generators, and nitrobenzylsulfonate-based acids. generators (nitrobenzyl derivatives), iminosulfonate-based acid generators, disulfone-based acid generators, and the like.

As a preferable sulfonium salt type acid generator, the compound represented by the following formula (c-1) is mentioned, for example.

[Formula 29]

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

Specifically, as A ^- , 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-toluene sulfonate, nonafluorobutane sulfonate, adamantane carboxylate, tetraaryl borate, fluorinated alkyl fluorophosphate anion represented by the following formula (c-2), and the like.

[Formula 30]

In the formula (c-2), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. n is the number and represents the integer of 1-5. n Rf's may be the same or different, respectively.

As the photoacid generator represented by the formula (c-1), 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfonium hexafluoroantimonate, 4-(2-chloro-4-benzoylphenyl Thio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-methylphenyl)sulfonium hexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-(β- Hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- ( 3-methyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-(2-fluoro4-benzoylphenylthio)phenylbis(4-fluorophenyl) Sulfonium hexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-(2,3,5,6 -Tetramethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-(2,6-dichloro-4-benzoylphenylthio)phenylbis(4-fluoro Phenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3 -Dimethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfonium Hexafluoroantimonate, 4-(3-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-fluoro4-benzoylphenylthio) Phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-( 2,3,5,6-tetramethyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-(2,6-dichloro-4-benzoylphenylthio)phenyl Bis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-(2,6-dimethyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-(2-chloro-4-acetylphenylthio)phenyldiphenylsulfonium hexafluoro Roantimonate, 4-(2-chloro-4-(4-methylbenzoyl)phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzoyl ) Phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- ( 2-chloro-4-dodecanoylphenylthio)phenyldiphenylsulfonium hexafluoroantimonate, 4-(2-chloro-4-acetylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoro Roantimonate, 4-(2-chloro-4-(4-methylbenzoyl)phenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis ( 4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4 -Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4 -(2-chloro-4-(4-methoxybenzoyl)phenylthio)phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-(2-chloro-4-dodecanoylphenylthio) Phenylbis(4-chlorophenyl)sulfonium hexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfonium hexafluorophosphate, 4-(2-chloro-4-benzoyl Phenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenyl alcohol Phonium trifluoromethanesulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluorophosphate, 4-(2-chloro-4-benzoylphenylthio) Phenylbis(4-fluorophenyl)sulfonium tetrafluoroborate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium perchlorate, 4-(2-chloro-4 -Benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumtrifluoromethanesulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium p-toluene Sulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumcamphorsulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluoro Rophenyl) sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl Phenylthio) phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro- 4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumtrifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]sulfoniumtrifluorotrispentafluoroethylphosphate, diphenyl[4 -(p-terphenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[4-(p-terphenylthio)phenyl]sulfonium trifluorotrispentafluoroethyl phosphate, etc. are mentioned.

Other onium salt-based acid generators include, for example, triphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert- butoxyphenyl)phenylsulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris (3-tert-butoxyphenyl)sulfonium, (3,4-ditert-butoxyphenyl)diphenylsulfonium, bis(3,4-ditert-butoxyphenyl)phenylsulfonium, tris(3, 4-ditert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tris(4-tert- butoxycarbonylmethyloxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, Dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium Sulfonium cations such as phonium, diphenyliodonium, bis(4-tert-butylphenyl)iodonium, (4-tert-butoxyphenyl)phenyliodonium, (4-methoxyphenyl)phenyliodonium, etc. What was substituted with iodonium cations, such as an aryliodonium cation of , is mentioned.

As the oxime sulfonate-based acid generator, [2-(propylsulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene](o-tolyl)acetonitrile, α-(p-toluene sul Phonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-( 2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and the like.

In addition to the above, compounds represented by the following formula (c-3) are exemplified.

[Formula 31]

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

R ^c5 is particularly preferably an aromatic compound group, and examples of the aromatic compound group include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and heterocyclic groups such as a furyl group and a thienyl group. These may have one or more suitable substituents, such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group, on the ring. Moreover, as ^Rc6 , an alkyl group having 1 to 6 carbon atoms is particularly preferred, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Moreover, the integer of 1-3 is preferable, and, as for r, 1 or 2 is more preferable.

Examples of the photoacid generator represented by the formula (c-3) include compounds in which R ^c5 is any of a phenyl group, a methylphenyl group, and a methoxyphenyl group and R ^c6 is a methyl group when r = 1. More specifically, as the photoacid generator represented by the formula (c-3), α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p- methylphenyl)acetonitrile, and α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile.

As the photo-acid generator represented by the formula (c-3), when r = 2, a photo-acid generator represented by the following formula is exemplified.

[Formula 32]

As the halogen-containing triazine compound, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2, 4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5 -Propyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2- (3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl] -s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloro Romethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl) )-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-(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-triazine, 2-[2-(2- Furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis ( Trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-tri Azine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxy Phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3- Halogen-containing triazine compounds such as dibromopropyl) -1,3,5-triazine, and halogens represented by the following formula (c-4) such as tris(2,3-dibromopropyl) isocyanurate A containing triazine compound is mentioned.

[Formula 33]

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

In addition, other photoacid generators include bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethyl) Sulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2, 4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylphenylsulfonyl)diazomethane, bis(3-methylphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, Bissulfonyldiazomethanes such as bis(4-fluorophenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, and bis(4-tert-butylphenylsulfonyl)diazomethane ; 2-Methyl-2-(p-toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2-methanesulfonyl-2-methyl-(p- sulfonylcarbonylalkanes such as methylthio)propiophenone and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one; 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarb Bornyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3- Dimethyl-2-butanone, 1-acetyl-1-(1-methylethylsulfonyl)diazomethane, 1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone , 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, 2-diazo Crude-2-(p-toluenesulfonyl)acetatecyclohexyl, 2-diazo-2-benzenesulfonylacetate-tert-butyl, 2-diazo-2-methanesulfonylacetate isopropyl, 2-diazo- sulfonylcarbonyldiazomethanes such as cyclohexyl 2-benzenesulfonylacetate and tert-butyl 2-diazo-2-(p-toluenesulfonyl)acetic acid; nitrobenzyl derivatives such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, and p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl; Methanesulfonic acid ester of pyrogallol, benzenesulfonic acid ester of pyrogallol, p-toluenesulfonic acid ester of pyrogallol, p-methoxybenzenesulfonic acid ester of pyrogallol, mesitylenesulfonic acid ester of pyrogallol, benzylsulfonic acid ester of pyrogallol, gallic acid Methanesulfonic acid ester of alkyl, benzenesulfonic acid ester of alkyl gallate, p-toluenesulfonic acid ester of alkyl gallate, p-methoxybenzenesulfonic acid ester of alkyl gallate (alkyl group has 1 to 15 carbon atoms), mesitylenesulfonic acid ester of alkyl gallate esters of polyhydroxy compounds and aliphatic or aromatic sulfonic acids, such as benzylsulfonic acid esters of alkyl gallate; etc. can be mentioned.

These photo-acid generators can be used individually or in combination of 2 or more types.

It is preferable that it is 0.05-30 mass parts with respect to 100 mass parts of alkali-soluble resin which has a phenolic hydroxyl group, and, as for content of a photo-acid generator, it is more preferable that it is 0.1-10 mass parts. By setting it as the said range, sclerosis|hardenability of the photosensitive resin composition becomes favorable.

As described above, the photosensitive resin composition of the second aspect contains the compound represented by the formula (1). This compound has good solubility in organic solvents, and when incorporated in a photosensitive resin composition, good micropatterning properties can be obtained.

It is preferable that it is 1-200 mass parts, and, as for content of the compound represented by said formula (1), it is more preferable that it is 10-80 mass parts with respect to 100 mass parts of said photo-acid generators. By setting it as the said range, favorable micropatterning characteristic can be obtained, obtaining good developability.

The photosensitive resin composition of the second aspect may further contain a compound having a molecular weight of less than 2000 having 4 or more phenolic hydroxyl groups.

Specifically as such a compound, bis[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-cyclo Hexyl-6-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -3,4-dihydroxyphenylmethane, etc. Hydroxyaryl type compound; 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-( bis(hydroxyphenyl)alkane compounds such as 2',4'-dihydroxyphenyl)propane; Poly(o-hydroxystyrene) with molecular weight less than 2000, poly(m-hydroxystyrene), poly(p-hydroxystyrene), poly(α-methyl-p-hydroxystyrene), poly(4-hydroxy -3-methylstyrene) and other polyhydroxystyrene-based compounds; etc. can be mentioned. These benzophenone-based compounds, hydroxyaryl-based compounds, bis(hydroxyphenyl)alkane-based compounds, and polyhydroxystyrene-based compounds may have substituents other than hydroxyl groups.

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

The content of the compound having a molecular weight of less than 2000 having 4 or more phenolic hydroxyl groups is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having phenolic hydroxyl groups. By setting it as the said range, the phenomenon which becomes thin toward the edge at the time of patterning the photosensitive resin composition can be suppressed.

As an organic solvent in the photosensitive resin composition of a 2nd aspect, the organic solvent illustrated in the photosensitive resin composition of a 1st aspect is mentioned.

The content of the organic solvent is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, so that the solid content concentration of the photosensitive resin composition of the second aspect is more preferable.

The photosensitive resin composition of a 2nd aspect may contain the said various additives as needed similarly to the photosensitive resin composition of a 1st aspect.

(3) The photosensitive resin composition of the third aspect

The photosensitive resin composition of the 3rd aspect is a negative photosensitive resin composition containing a photosensitive polyimide precursor, a photopolymerizable monomer, a photoinitiator, the compound represented by said formula (1), and an organic solvent.

As the photosensitive polyimide precursor in the photosensitive resin composition of the third aspect, for example, one having a structural unit represented by the following formula (d-1) and having an acid functional group and a photosensitive group in the molecule can be used.

[Formula 34]

In the formula (d-1), X ^d represents a tetravalent organic group containing no atom having an unshared electron pair in the backbone that binds the two amide groups bonded to X ^d , and Y ^d represents 2 bonded to Y ^d Represents a divalent organic group containing no atom having an unshared electron pair in the backbone binding the two amide groups, and R ^d1 and R ^d2 each independently represent a hydroxyl group or a monovalent organic group.

In the definition of X ^d and Y ^d , "skeleton binding two amide groups" refers to a skeleton composed only of atoms constituting a chain of bonds binding two amide bonds. Therefore, an atom such as a hydrogen atom or a fluorine atom, which exists as a terminal and does not form a chain of bonds binding two amide bonds, is not included in the above "skeleton". However, when atoms constituting a ring (aromatic ring or aliphatic ring) are included in the skeleton, all atoms constituting the ring are included in the above "skeleton". For example, when a benzene ring or a cyclohexyl ring is included, six carbon atoms constituting the benzene ring or cyclohexyl ring itself are included in the "skeleton". Substituents and hydrogen atoms bonded to the benzene ring or cyclohexyl ring are not included in the "skeleton" herein.

Therefore, when there is a carbonyl bond on the backbone, only the carbon atoms in the carbonyl group constitute the chain binding the two amide groups, so the oxygen atoms in the carbonyl group do not constitute the above-mentioned "backbone". . In addition, for a 2,2-propylidene bond or a hexafluoro-2,2-propylidene bond, only the carbon atom present in the center (position 2) constitutes the backbone, and the carbon atoms at both ends (position 1 or 3 position) is not regarded as constituting the above "skeleton". Examples of the "atom having an unshared electron pair" include an oxygen atom, a nitrogen atom, and a sulfur atom, while examples of the "atom having no unshared electron pair" include a carbon atom, a silicon atom, and the like.

In the photosensitive polyimide precursor, if X ^d does not contain an atom having an unshared electron pair in the backbone as described above, it is preferable because there is little swelling during alkali development. For the same reason, Y ^d also preferably does not contain an atom having an unshared electron pair in its backbone.

In addition, in the photosensitive polyimide precursor, higher substrate adhesion can be imparted if there is one having Y ^d2 containing a silicon atom as a part instead of Y ^d in the structural unit, for example, one containing a siloxane bond. desirable because there is In this case, it is preferable that the ratio is 1 to 20 mol% of all the diamine residues forming the photosensitive polyimide precursor.

As ^Xd and ^Yd in the formula (d-1), an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group, an aromatic ring such as a benzene ring having 6 to 20 carbon atoms and a naphthalene ring, and two of these aromatic rings Preferable examples include those in which 10 to 10 are bonded via a single bond, an alkylene group, a fluorinated alkylene group, a carbonyl group, or the like. Moreover, these may have substituents, such as a hydrocarbon group, a halogenated hydrocarbon group, and a halogen atom, on an aromatic ring. In addition, among these X ^d and Y ^d , it is preferable that the atom directly bonded to the atom constituting the skeleton is also an "atom having no unshared electron pair" because its effect is high. Note that this definition excludes those where an oxygen atom is directly bonded to a carbon atom constituting a skeleton, such as a carbonyl group, and a fluorine atom bonded to a carbon atom constituting a skeleton. Moreover, it is preferable that X ^d and Y ^d do not contain a fluorine atom.

A carboxyl group, a phenolic hydroxyl group, a sulfonic acid group etc. are mentioned as an acid functional group contained in the molecule|numerator of the photosensitive polyimide precursor, Among these, a carboxyl group is preferable. In addition, as the photosensitive group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloxy group, a methacryloxy group, etc. containing an ethylenically unsaturated bond are preferable, and among them, an acryloyl group and a methacrylic group. A loyl group, an acryloxy group, and a methacryloxy group are preferable.

In the photosensitive polyimide precursor, the acid functional group is present as R ^d1 or R ^d1 in the structural unit of the formula (d-1) as a hydroxyl group (ie, a carboxyl group is formed), or as Y ^d It is preferable to make it exist in the diamine residue shown. In addition, the photosensitive group is present as a group bonded to an aromatic ring of a diamine residue having an aromatic ring, for example, among diamine residues represented by the side chain represented by ^Rd1 or ^Rd2 in the formula (d-1) or ^Yd . it is desirable

Examples of the monovalent organic group having a photosensitive group for ^Rd1 and ^Rd2 include those represented by the following formulas.

[Formula 35]

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.

Moreover, in ^Rd1 and ^Rd2 , as a monovalent organic group which does not have a photosensitive group, a C1-C15 alkoxy group, an alkylamino group, etc. are mentioned.

As a photosensitive polyimide precursor, what has 50-100 mol% of structural units represented by the said formula (d-1) is preferable, and has only the structural unit represented by the said formula (d-1), or the said formula (d- It is more preferable to have a structural unit represented by 1) and a structural unit in which Y ^d in the formula (d-1) is a divalent organic group containing a silicon atom.

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

Examples of tetracarboxylic dianhydride include ^pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10- Perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 4,4'-hexafluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

As diamine, Y ^d is given, for example, 2,2'-dimethyl-4,4'-diaminobiphenyl, 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-xylylenediamine, m-xylylenediamine, 4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis-(2,6-diisopropylaniline), 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'-hexafluoro Rodimethyl-4,4'-diaminobiphenyl, 3,3'-hexafluorodimethyl-4,4'-diaminobiphenyl, 4,4'-hexafluoroisopropylidenedianiline, 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-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4,6-trimethyl-1,3-phenylenediamine, 2,7-diaminofluorene, Preferable examples include 4,4-diaminooctafluorobiphenyl, 2,2-hexafluorodimethyl-4,4'-diaminobiphenyl, and the like, and these diamines can be used alone or in combination of two or more. .

In addition, Y ^d may have at least one phenolic hydroxyl group or carboxyl group as an acid functional group, as long as it is a bifunctional amine containing no atoms having unshared electron pairs in the backbone binding the amino group. For example, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis(4-amino-3-carboxyphenyl)methylene, 4 ,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-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, etc. are mentioned as preferable examples. These are used individually or in combination of 2 or more types together with diamine.

Moreover, as what provides ^Y2d containing a silicon atom, aliphatic diamine, such as diamino polysiloxane represented by the following formula (d-2), can be illustrated.

[Formula 36]

In said formula (d-2), s, t, and u respectively independently represent the integer of 1-10.

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

In order to make a polyimide precursor having a photosensitive group, for example, a compound having an ethylenically unsaturated bond and an amino group or a quaternary salt group thereof is ionically bonded at a carboxyl group of polyamic acid and an amino group or a quaternary salt group thereof. The method of using the shown polyimide precursor, the method of introduce|transducing an ethylenically unsaturated bond into a side chain through covalent bonds, such as an ester bond and an amide bond, etc. are mentioned.

Among these, a photosensitive polyimide precursor (polyamic acid ester) having an ethylenically unsaturated bond introduced into an ester bond is particularly preferable for alkali development. In the case of introducing an ethylenically unsaturated bond into an ester bond, the amount of the compound having an ethylenically unsaturated bond introduced is 85 to 25 moles relative to the total amount of carboxyl groups of the polyamic acid from the viewpoint of alkali solubility, curability, heat resistance, and reactivity. It is preferable to set it as an amount used as %, and to set the remainder as a carboxyl group (ie, polyamic acid partial ester).

Examples of the compound introducing an ethylenically unsaturated bond via an ester bond include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2-(methacryloyl yloxy) ethyl ester, dicaprolactone 2-(methacryloyloxy) ethyl ester, caprolactone 2-(acryloyloxy) ethyl ester, dicaprolactone 2-(acryloyloxy) ethyl ester, etc. can

It is preferable that the mass average molecular weight of the photosensitive polyimide precursor is 5000-80000.

It is preferable that it is 40-95 mass % with respect to solid content of the photosensitive resin composition of a 3rd aspect, and, as for content of a photosensitive polyimide precursor, it is more preferable that it is 55-90 mass %. By setting it as the said range, there exists a tendency for easy balance of developability.

As a photopolymerizable monomer in the photosensitive resin composition of a 3rd aspect, the photopolymerizable monomer illustrated in the photosensitive resin composition of a 1st aspect is mentioned.

It is preferable that it is 5-100 mass parts with respect to 100 mass parts of photosensitive polyimide precursors, and, as for content of a photopolymerizable monomer, it is more preferable that it is 5-40 mass parts. By setting it as the said range, it tends to be easy to balance sensitivity, developability, and resolution.

As a photoinitiator in the photosensitive resin composition of a 3rd aspect, the photoinitiator illustrated in the photosensitive resin composition of a 1st aspect is mentioned.

It is preferable that content of a photoinitiator is 0.01-40 mass parts with respect to 100 mass parts of photosensitive polyimide precursors. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained, and also the ability to form a coating film can be improved and curing failure can be suppressed.

As described above, the photosensitive resin composition of the third aspect contains the compound represented by the formula (1). This compound has good solubility in organic solvents, and when incorporated in a photosensitive resin composition, good micropatterning properties can be obtained.

It is preferable that it is 0.5-50 mass % in the said solid content, and, as for content of the compound represented by said Formula (1), it is more preferable that it is 1-20 mass %. By setting it as the said range, favorable micropatterning characteristic can be obtained, obtaining favorable developability.

As an organic solvent in the photosensitive resin composition of a 3rd aspect, the organic solvent illustrated in the photosensitive resin composition of a 1st aspect is mentioned. Among these, a polar solvent that completely dissolves the polyimide to be produced is preferable. Such polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphate triamide, and γ-butyl Lactone etc. are mentioned.

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

The photosensitive resin composition of a 3rd aspect may contain said various additives as needed similarly to the photosensitive resin composition of a 1st aspect.

(4) The photosensitive resin composition of the fourth aspect

The photosensitive resin composition of the 4th aspect contains the polyimide precursor, the compound represented by said formula (1), and the organic solvent. It is also preferable to contain a photosensitizer.

As a polyimide precursor in the photosensitive resin composition of a 4th aspect, the polyamic acid which has a structural unit represented by following formula (e-1) can be used, for example.

[Formula 37]

In the formula (e-1), ^Ree1 represents a tetravalent organic group, ^Re2 represents a divalent organic group, and ^Re3 and ^Re4 represent a hydrogen atom or a monovalent organic group.

When R ^e3 and R ^e4 are monovalent organic groups, 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 thereto, etc. can be heard

As the polyimide precursor, a polyamic acid in which ^Re3 and ^Re4 are hydrogen atoms is preferably used in terms of alkali developability.

In addition, although the quaternary value of R ^e1 represents only the valence required for bonding with an acid, it may further have a substituent other than that. Similarly, although the divalent R ^e2 represents only the valence required for bonding with an amine, it may have additional substituents.

Polyamic acid is obtained by the reaction of acid dianhydride and diamine, but in terms of imparting excellent heat resistance and dimensional stability to the finally obtained polyimide, in the formula (e-1), Re ^e1 or Re ^e2 is an aromatic group. is preferred, and it is more preferred that R ^e1 and R ^e2 are aromatic groups. At this time, in R ^e1 of the formula (e-1), the four groups ((-CO-) ₂ (-COOH) ₂ ) bonded to R ^e1 may be bonded to the same aromatic ring, or in different directions. You may couple|bond with the ring. Similarly, in ^Re2 of the formula (e-1), the two groups ((-NH-) ₂ ) bonded to ^Re2 may be bonded to the same aromatic ring or to different aromatic rings. do.

The polyamic acid represented by the formula (e-1) may consist of a single structural unit or may consist of two or more types of repeating units.

As a method of manufacturing a polyimide precursor, a conventionally well-known method is applicable. For example, (1) a method of synthesizing polyamic acid as a precursor from acid dianhydride and diamine, (2) ester acid or amide synthesized by reacting acid dianhydride with a monohydric alcohol, amino compound, epoxy compound, etc. Although the method of making a diamino compound or its derivative(s) react with the carboxylic acid of an acid monomer, and synthesize|combining a polyimide precursor etc. is mentioned, it is not limited to this.

As the acid dianhydride applicable to the reaction for obtaining the polyimide precursor, for example, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic Aliphatic tetracarboxylic dianhydride, such as acid dianhydride and cyclopentane tetracarboxylic dianhydride; Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3',3 ,4'-benzophenonetetracarboxylic 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-di Carboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone 2 Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane 2 Anhydride, bis(2,3-dicarboxyphenyl)methane 2 Anhydride, bis(3,4-dicarboxyphenyl)methane 2 Anhydride, 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-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 1,4-bis[(3,4-dicarboxy )benzoyl]benzene dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{4-[3-(1,2 -dicarboxy)phenoxy]phenyl}propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-di Carboxy)phenoxy]phenyl}ketone dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3-(1,2- Dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy) Phenoxy]phenyl}ketone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy ]phenyl}sulfone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy] Phenyl} sulfide 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-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracentetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetra Carboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarb Aromatic tetracarboxylic dianhydride, such as boxylic dianhydride, etc. are mentioned.

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

As diamine applicable to the reaction for obtaining a polyimide precursor, for example, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diamino Diphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane , 2,2-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2- Di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-di(4-aminophenyl)-1,1,1,3,3,3-hexa Fluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-di(3-aminophenyl) -1-phenylethane, 1,1-di(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, 1,3- Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-amino Benzoyl)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-ditrifluoromethylbenzene ) Benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1 ,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine , 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[ 4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-( 3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy) ) phenyl] 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)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene , 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3- Aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[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)benzoyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-) Amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone, 3,3'-diamino-4,4 '-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino- 4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindan, 6,6'-bis aromatic amines such as (4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindan; 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω -Bis (3-aminobutyl) polydimethylsiloxane, 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-amino Ethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-amino Propyl) 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-diaminononane, 1,10-diaminodecane, 1,11- aliphatic amines such as diaminoundecane and 1,12-diaminododecane; 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di(2-aminoethyl)cyclohexane, 1,3-di(2-amino Ethyl)cyclohexane, 1,4-di(2-aminoethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,5 - Alicyclic diamines such as bis(aminomethyl)bicyclo[2.2.1]heptane; etc. can be mentioned. Diamines in which some or all of the hydrogen atoms on the aromatic ring of the diamine are substituted with substituents selected from the group consisting of fluoro, methyl, methoxy, trifluoromethyl and trifluoromethoxy can also be used.

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

It is preferable that it is 50-99 mass % with respect to solid content of the photosensitive resin composition of a 4th aspect, and, as for content of a polyimide precursor, it is more preferable that it is 70-95 mass %. By setting it as the said range, coating film formation ability can be improved.

As described above, the photosensitive resin composition of the fourth aspect contains the compound represented by the formula (1). This compound has good solubility in organic solvents, and when incorporated in a photosensitive resin composition, good micropatterning properties can be obtained.

It is preferable that content of the compound represented by said Formula (1) is 0.01-40 mass parts with respect to 100 mass parts of polyimide precursors. By setting it as the said range, favorable micropatterning characteristic can be obtained, obtaining favorable developability.

As an organic solvent in the photosensitive resin composition of a 4th aspect, the organic solvent illustrated in the photosensitive resin composition of a 1st aspect is mentioned. Among these, propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ - Polar solvents such as butyrolactone, aromatic hydrocarbons such as toluene, and mixed solvents thereof are preferred.

The content of the organic solvent is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, so that the solid content concentration of the photosensitive resin composition of the fourth aspect is more preferable.

When the photosensitive resin composition of the 4th aspect is a positive photosensitive resin composition, it is preferable to further contain a photoacid generator as a photosensitive agent. As a photo-acid generator, a quinonediazide group-containing compound other than what was mentioned above in the photosensitive resin composition of a 2nd aspect is mentioned. Examples of the quinonediazide group-containing compound include orthoquinonediazide compounds and diazonaphthoquinone compounds. esters or partial esters; Orthoquinonediazide compounds (especially 1,1-bis(4-hydroxyphenyl)-1-[ An ester compound obtained by reaction of 4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride is preferred) etc. are preferred.

Other components, such as a thermal crosslinking agent, a silicon-containing compound, a non-polymerizable binder polymer, a solvent, an elastomer, a dissolution promoter, a dissolution inhibitor, a surfactant or leveling agent, and a thermal acid generator, may be contained as necessary.

The thermal crosslinking agent is not particularly limited, except that it is a compound that crosslinks or polymerizes in the step of heat treatment after development, but is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group or a vinyl ether group in the molecule. For example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3,5-benzenedimethanol, 4,4-biphenyldimethanol, 2,6 - Compounds having methylol groups such as pyridine dimethanol, 2,6-bis(hydroxymethyl)-p-cresol, and 4,4'-methylenebis(2,6-dialkoxymethylphenol); 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)bi having an alkoxymethyl group such as phenyl, 3,3'-bis(methoxymethyl)biphenyl, 2,6-naphthalenedicarboxylic acid methyl, and 4,4'-methylenebis(2,6-dimethoxymethylphenol); compound; Methylolmelamine compounds such as hexamethylolmelamine and hexabutanolmelamine, alkoxymelamine compounds such as hexamethoxymelamine, alkoxymethylglycoluril compounds such as tetramethoxymethylglycoluril, methylolbenzoguanamine compounds, and dimethylolethyleneurea methylolurea compounds such as the like; cyano compounds from dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid and the like; isocyanate compounds such as 1,4-phenylene diisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; Ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolac epoxy group-containing compounds such as resin type epoxy resins; maleimide compounds such as N,N'-1,3-phenylenedimaleimide and N,N'-methylenedimaleimide; and the like, but are not limited thereto. These thermal cross-linking agents can be used alone or in combination of two or more.

Examples of the silicon-containing compound include silicon-containing resins, silicon-containing resin precursors, and silane coupling agents, with silane coupling agents being preferred, and 1-(2pyridyl)-3-[3-(trimethoxysilyl) A ureide group-containing silane coupling agent such as propyl] urea or 1-(3pyridyl)-3-[3-(triethoxysilyl)propyl]urea is more preferable.

When the photosensitive resin composition of the 4th aspect is a negative photosensitive resin composition, it is preferable to further contain a photobase generator as a photosensitizer. Although it does not specifically limit as a photobase generator, The thing similar to the oxime ester compound mentioned above in the photosensitive resin composition of a 1st aspect is mentioned preferably.

The negative photosensitive resin composition can contain the same other components as the positive photosensitive resin composition as needed.

It is as follows about the ratio of each component other than the compound represented by the said Formula (1) in the photosensitive resin composition of a 4th aspect.

It is preferable that it is 50 mass % or more with respect to the whole solid content of the photosensitive composition, and, as for content of a polyimide precursor, it is more preferable that it is 60-90 mass %.

The content of the photosensitizer is preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyimide precursor, from points such as sensitivity.

As for content in the case of containing a thermal crosslinking agent, 1-50 mass parts is preferable with respect to 100 mass parts of polyimide precursors.

It is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of polyimide precursors, and, as for content in the case of containing a silane compound, it is more preferable to set it as 1-10 mass parts.

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 a 4th aspect may contain said various additives as needed similarly to the photosensitive resin composition of a 1st aspect.

(5) The photosensitive resin composition of the fifth aspect

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

Examples of the epoxy resin in the photosensitive resin composition of the fifth aspect include a bisphenol A-type epoxy resin derived from bisphenol A and epichlorohydrin, a bisphenol F-type epoxy resin derived from bisphenol F and epichlorohydrin, Bisphenol S type epoxy resin, phenol novolac 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 Polyfunctional type epoxy resins such as non-non-type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, fluorene type epoxy resins, trifunctional type epoxy resins and tetrafunctional type epoxy resins, glycidyl ester type epoxy resins, glycidyl An amine type epoxy resin, a hydantoin type epoxy resin, an isocyanurate type epoxy resin, an aliphatic chain type epoxy resin, etc. are mentioned. These epoxy resins may 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 Resin, and Epiclon manufactured by DIC. 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Corporation, Celoxide series manufactured by Daicel (2021, 2021P, 2083, 2085, 3000, etc.), EPOLID series, EHPE series, Shinnit YD series, YDF series, YDCN series, YDB series manufactured by Tetsu Chemical Co., Ltd., phenoxy resin (polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, having epoxy groups at both ends; YP series, etc.), Nagase Chem Although the Denacol series by Tex Co., Ltd., the Epolite series by Kyoeisha Chemical Co., Ltd., etc. are mentioned, it is not limited to these.

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

It is preferable that it is 55-99 mass % with respect to solid content of the photosensitive resin composition of a 5th aspect, and, as for content of an epoxy resin, it is more preferable that it is 70-95 mass %. By setting it as the said range, coating film formation ability can be improved.

As described above, the photosensitive resin composition of the fifth aspect contains the compound represented by the formula (1). This compound has good solubility in organic solvents, and when incorporated in a photosensitive resin composition, good micropatterning properties can be obtained.

It is preferable that content of the compound represented by said formula (5) is 1-30 mass parts with respect to 100 mass parts of epoxy resins. By setting it as the said range, favorable micropatterning characteristic can be obtained, obtaining good developability.

As an organic solvent in the photosensitive resin composition of a 5th aspect, the organic solvent illustrated in the photosensitive resin composition of a 1st aspect is mentioned. Among these, propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ - Polar solvents such as butyrolactone, aromatic hydrocarbons such as toluene, and mixed solvents thereof are preferred.

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

The photosensitive resin composition of a 5th aspect may contain the said various additives as needed similarly to the photosensitive resin composition of a 1st aspect.

In addition, the epoxy group-containing polycarboxylic acid resin in the sixth aspect described later is not limited to that all epoxy groups are consumed by reaction with "monocarboxylic acid having an alcoholic hydroxyl group" and "polybasic acid anhydride", It also corresponds to the epoxy resin in the photosensitive resin composition of the 5th aspect in that it has an epoxy group which normally remains. In this regard, as the epoxy resin in the photosensitive resin composition of the fifth aspect, an epoxy group-containing polycarboxylic acid resin in the photosensitive resin composition of the sixth aspect can be used in some cases. In the present specification, among the epoxy resins in the photosensitive resin composition of the fifth aspect, non-carboxylic acid-modified epoxy resins other than the epoxy group-containing polycarboxylic acid resin in the photosensitive resin composition of the sixth aspect are referred to as non-carboxylic acid-modified epoxy resins. there is.

(6) The photosensitive resin composition of the 6th 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 formula (1), and an organic solvent.

As 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 a monocarboxylic acid having one or more alcoholic hydroxyl groups in one molecule. What is obtained by making a polybasic acid anhydride react further can be used for the reactant obtained by making it react.

Examples of the epoxy compound having two or more epoxy groups in one molecule include novolac type epoxy resins, bisphenol type epoxy resins, trisphenolmethane type epoxy resins, tris(2,3-epoxypropyl) isocyanurate, and Phenyl diglycidyl ether, an alicyclic epoxy resin, a copolymerization type epoxy resin, etc. are mentioned.

Examples of the novolac-type epoxy resin include a reaction between novolaks obtained by reacting formaldehyde with phenols such as phenol, cresol, halogenated phenol, and alkylphenol in the presence of an acidic catalyst, and epichlorohydrin or methyl epichlorohydrin. and the like obtained by doing. As a commercial item, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1027, EPPN-201, BREN-S (all are made by Nippon Chemical Co., Ltd.); DEN-431, DEN-439 (both manufactured by Dow Chemical Co.); N-730, N-770, N-865, N-665, N-673, and VH-4150 (all manufactured by Dainippon Ink and Chemicals 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 tetrabrombisphenol A with epichlorohydrin and methyl epichlorohydrin, and bisphenol A and bisphenol F. What is obtained by making diglycidyl ether, the condensate of the said bisphenol, epichlorohydrin, or methyl epichlorohydrin react is mentioned. As a commercial item, Epicoat 1004, Epicoat 1002, Epicoat 4002, Epicoat 4004 (all are Yuka Shell Epoxy Co., Ltd. make), etc. are mentioned.

As a trisphenolmethane type epoxy resin, what is obtained by making trisphenolmethane, triscrezolmethane, epichlorohydrin, and methyl epichlorohydrin react, etc. are mentioned, for example. As a commercial item, EPPN-501, EPPN-502 (all Nippon Chemical Co., Ltd. make), etc. are mentioned.

As an alicyclic epoxy resin, Celloxide 2021 by the Daicel Chemical Industry Co., Ltd.; Epomic VG-3101 manufactured by Mitsui Petrochemical Industry; E-1031S by Yuka Shell Epoxy Co., Ltd., EPB-13 by Nippon Soda Co., Ltd., EPB-27, etc. are mentioned. In addition, as a copolymerization type epoxy resin, CP-50M, CP-50S manufactured by Nippon Oil Co., Ltd., which is a copolymer of glycidyl methacrylate, styrene, and α-methylstyrene, or glycidyl methacrylate and cyclohexylmaleimide Copolymers, such as these, etc. are mentioned.

Among these epoxy resins having two or more epoxy groups in one molecule, particularly preferred ones include, for example, cresol novolak type epoxy resins, phenol novolak type epoxy resins, bisphenol type epoxy resins, and trisphenolmethane type epoxy resins. there is. In particular, polycondensates of α-hydroxyphenyl-ω-hydropoly(biphenyldimethylene-hydroxyphenylene) and 1-chloro-2,3-epoxypropane, and α-2,3-epoxypropoxyphenyl- ω-hydropoly{2-(2,3-epoxypropoxy)-benzylidene-2,3-epoxypropoxyphenylene} is preferred.

Examples of monocarboxylic acids having at least one alcoholic hydroxyl group in one molecule include hydroxyl such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproic acid, and hydroxypivalic acid. Monocarboxylic acids are mentioned. Among these, the monocarboxylic acid which has 1-5 alcoholic hydroxyl groups in 1 molecule is preferable.

Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. .

The reaction between the epoxy compound and the monocarboxylic acid is preferably from 0.1 to 0.7 mol, more preferably from 0.2 to 0.5 mol of the monocarboxylic acid per 1 equivalent of the epoxy group of the epoxy compound. In this reaction, it is preferable to use an organic solvent that does not react with an epoxy compound or a polybasic acid anhydride and does not have a hydroxyl group or a carboxyl group. In addition, a catalyst (for example, triphenylphosphine, benzyldimethylamine, trialkylammonium chloride, triphenylstibin, etc.) can be used to promote the reaction. In the case of using a catalyst, inactivation of the catalyst using an organic peroxide or the like after completion of the reaction is preferable because it is stable and has good storage properties. The amount of the reaction catalyst used is preferably 0.1 to 10% by weight relative to the reaction mixture, and the reaction temperature is preferably 60 to 150°C. Thereby, the reaction product of the said epoxy compound and the said monocarboxylic acid can be obtained.

In the reaction between this reactant and the polybasic acid anhydride, it is preferable to react the polybasic acid anhydride in an amount such that the finally obtained polycarboxylic acid resin having an epoxy group has an acid value of 50 to 150 mgKOH/g. As for reaction temperature, 60-150 degreeC is preferable. In this way, an epoxy group-containing polycarboxylic acid resin can be obtained.

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

It is preferable that it is 30-80 mass % with respect to solid content of the photosensitive resin composition of a 6th aspect, and, as for content of epoxy-group-containing polycarboxylic acid resin, it is more preferable that it is 40-70 mass %. By setting it as the said range, coating film formation ability can be improved.

As a photo-acid generator in the photosensitive resin composition of a 6th aspect, the photo-acid generator illustrated in the photosensitive resin composition of a 2nd aspect is mentioned.

It is preferable that it is 0.5-30 mass % with respect to solid content of the photosensitive resin composition of a 6th aspect, and, as for content of a photo-acid generator, it is more preferable that it is 1-20 mass %. By setting it as the said range, sclerosis|hardenability of the photosensitive resin composition becomes favorable.

As described above, the photosensitive resin composition of the sixth aspect contains the compound represented by the formula (1). This compound has good solubility in organic solvents, and when incorporated in a photosensitive resin composition, good micropatterning properties can be obtained.

It is preferable that it is 1-500 mass parts, and, as for content of the compound represented by said formula (1), it is more preferable that it is 50-300 mass parts with respect to 100 mass parts of said photo-acid generators. By setting it as the said range, favorable micropatterning characteristic can be obtained, obtaining favorable developability.

The photosensitive resin composition of the 6th aspect may contain the sensitizer further. As the sensitizer, anthracene compounds (9,10-dialkoxy-anthracene derivatives) having alkoxy groups at the 9-position and 10-position are preferable, for example. As an alkoxy group, a C1-C4 alkoxy group is mentioned. The 9,10-dialkoxy-anthracene derivative may further have a substituent. As a substituent, a halogen atom, a C1-C4 alkyl group, a sulfonic acid alkyl ester group, a carboxylic acid alkyl ester group, etc. are mentioned. Examples of the alkyl group in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include alkyl groups having 1 to 4 carbon atoms. As for the substitution position of these substituents, the 2-position is preferable.

9,10-dialkoxy-anthracene derivatives include, for example, 9,10-dimethoxy-anthracene, 9,10-diethoxy-anthracene, 9,10-dipropoxy-anthracene, 9,10-dimethoxy- 2-ethyl-anthracene, 9,10-diethoxy-2-ethyl-anthracene, 9,10-dipropoxy-2-ethyl-anthracene, 9,10-dimethoxy-2-chloro-anthracene, 9,10- Dimethoxy anthracene-2-sulfonic acid methyl ester, 9,10-diethoxy anthracene-2-sulfonic acid methyl ester, 9,10-dimethoxy anthracene-2-carboxylic acid methyl ester, etc. are mentioned.

These compounds are obtained by treating anthraquinone derivatives with reducing agents such as zinc powder, hydrosulfite, palladium-carbon, and sodium borohydride in aqueous alkali solution to obtain 9,10-dihydroxyanthracene derivatives. After that, sulfuric acid esters such as dimethyl sulfuric acid and diethyl sulfuric acid, toluenesulfonic acid esters such as methyl toluenesulfonate, ethyl toluenesulfonate, propyl toluenesulfonate, and toluenesulfonic acid monoethylene glycol ester, or methyl benzenesulfonate, ethyl benzenesulfonate, propyl benzenesulfonate, etc. It is obtained by alkoxylating the 9 and 10 positions with a benzenesulfonic acid ester of

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

It is preferable that it is 0.1-6, and, as for content of a sensitizer, it is more preferable that it is 0.2-4 in a molar ratio with respect to the said photo-acid generator. By setting it as the said range, the sensitivity and sclerosis|hardenability of the photosensitive resin composition become favorable.

The photosensitive resin composition of the sixth aspect may further contain a modifying component for adjusting moisture resistance, heat resistance, adhesion, and the like. This modifying component itself may be cured by heat or ultraviolet rays, or may react with residual hydroxyl groups or carboxyl groups of the epoxy group-containing polycarboxylic acid resin by heat or ultraviolet rays. Specifically, epoxy compounds having at least one epoxy group in one molecule, melamine derivatives (eg, hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, etc.), bisphenol A-based compounds (eg, tetramethylol bisphenol A etc.), oxazoline compounds, etc. are mentioned.

Examples of the epoxy compound having at least one epoxy group per molecule include Epicoat 1009 and 1031 (all manufactured by Yuka Shell Co., Ltd.), Epiclon N-3050 and N-7050 (all manufactured by Dainippon Ink & Chemicals Co., Ltd.), DER-642U, and DER. -bisphenol A type epoxy resins such as 673MF (both manufactured by Dow Chemical Co.); hydrogenated bisphenol A-type epoxy resins such as ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd.); bisphenol F-type epoxy resins such as YDF-2004 and YDF-2007 (both manufactured by Tohto Kasei Co., Ltd.); brominated bisphenol A type epoxy resins such as SR-BBS, SR-TBA-400 (both manufactured by Sakamoto Chemical Industry Co., Ltd.), YDB-600 and YDB-715 (both manufactured by Toto Kasei Co., Ltd.); Novolak-type epoxy resins, such as EPPN-201, EOCN-103, EOCN-1020, and BREN (all Nippon Chemical Co., Ltd. make); Novolak-type epoxy resins of bisphenol A, such as Epiclon N-880 by Dainippon Ink and Chemicals; rubber-modified epoxy resins such as Epiclon TSR-601 manufactured by Dainippon Ink and Chemicals Co., Ltd. and R-1415-1 manufactured by A.C.R.; Bisphenol S-type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd., and Epiclon EXA-1514 by Dainippon Ink & Chemicals Co., Ltd.; diglycidyl terephthalates such as Blemmer DGT manufactured by Nippon Oil & Oil Co.; triglycidyl isocyanurates such as TEPIC manufactured by Nissan Chemical Industries, Ltd.; non-ylenol-type epoxy resins such as YX-4000 manufactured by Yuka Shell; Bisphenol-type epoxy resins, such as YL-6056 by the Yuka Shell company; Alicyclic epoxy resins, such as Celloxide 2021 by Daicel Chemical Industry Co., Ltd.; etc. can be mentioned.

It is preferable that it is 50 mass % or less with respect to solid content of the photosensitive resin composition of a 6th aspect, and, as for content of a modifying component, it is more preferable that it is 30 mass % or less.

The photosensitive resin composition of the sixth aspect further contains known fillers such as barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide and mica in order to improve properties such as adhesion and hardness. may contain.

It is preferable that it is 60 mass % or less with respect to solid content of the photosensitive resin composition of a 6th aspect, and, as for content of a filler, it is more preferable that it is 5-40 mass %.

The photosensitive resin composition of the sixth aspect further comprises coloring agents such as phthalocyanine blue, phthalocyanine green, disazo yellow, crystal violet, titanium oxide, and carbon black, thickeners such as ultrafine silica and montmorillonite, antifoaming agents such as silicone-based polymers and fluorine-based polymers, and /or You may contain additives, such as an adhesive imparting agent, such as a leveling agent and a silane coupling agent.

As an organic solvent in the photosensitive resin composition of a 6th aspect, the organic solvent illustrated in the photosensitive resin composition of a 1st aspect is mentioned.

The content of the organic solvent is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, so that the solid content concentration of the photosensitive resin composition of the sixth aspect is more preferable.

The photosensitive resin composition of a 6th aspect may contain said various additives as needed similarly to the photosensitive resin composition of a 1st aspect.

<Preparation method of photosensitive resin composition>

The photosensitive resin composition according to the present invention is prepared by mixing the above components with a stirrer. Moreover, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.

≪Pattern formation method≫

The pattern formation method according to the present invention is to form a coating film or a molded body using the photosensitive resin composition according to the present invention, irradiate the coated film or molded body with electromagnetic waves in a predetermined pattern, and develop.

More specifically, first, a coating film or molded body is formed by an appropriate coating method or molding method. For example, by applying a photosensitive resin composition on a substrate using a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater, and drying the , a coating film can be formed. The drying method is not particularly limited. For example, (1) a method of prebaking on a hot plate at a temperature of 80 to 120°C, preferably 90 to 100°C for 60 to 120 seconds, (2) several hours at room temperature - a method of leaving it for several days, (3) a method of removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours, and the like.

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

Next, the coated film or molded body after exposure is patterned into a desired shape by developing with a developing solution. 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 developing solution include organic solutions such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

About the pattern after development, it is preferable to post-bake at about 200-250 degreeC.

≪Cured film, insulating film, color filter, display device≫

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

For example, a transparent cured film or an insulating film can be obtained by forming a coating film using a photosensitive resin composition not containing a coloring agent, and irradiating and/or heating the coating film with electromagnetic waves. Such a cured film or insulating film is used as a flattening film for, for example, a liquid crystal display or an organic EL display or as an interlayer insulating film.

In addition, this cured film and insulating film may be patterned. As described above, a patterned cured film and an insulating film can be obtained by irradiating and developing the coated film with electromagnetic waves in a predetermined pattern. The patterned cured film is used, for example, as spacers and barrier ribs in liquid crystal displays and organic EL displays.

Further, a coating film is formed using a photosensitive resin composition containing a coloring agent (particularly the photosensitive resin composition of the first aspect), the coating film is irradiated with electromagnetic waves in a predetermined pattern and developed, for example, a liquid crystal display It is also possible to form a pixel or a black matrix of a color filter of .

A display device according to the present invention includes such a cured film, an insulating film, and a color filter. As a display device, a liquid crystal display, an organic electroluminescent display, etc. are mentioned.

Example

Hereinafter, the present invention will be described in more detail by showing examples, but the scope of the present invention is not limited to these examples.

<Compounds and Comparative Compounds Represented by Formula (1)>

As a compound represented by said formula (1), the compounds 1-2 represented by the following formula were prepared. The synthesis method of these compounds 1-2 is shown below. For comparison, Comparative Compounds 1 to 3 represented by the following formulas were prepared.

[Formula 38]

[Formula 39]

[Synthesis of Compound 1]

First, 30 g of a cinnamic acid derivative having the structure shown below was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to the methanol. Then, the methanol solution was stirred at 40°C. Methanol was distilled off, and the residue was suspended in 200 g of water. 200 g of tetrahydrofuran was mixed and stirred with the obtained suspension, and the aqueous phase was separated. Under ice-cooling, after adding and stirring 4 g of hydrochloric acid, 100 g of ethyl acetate was mixed and stirred. After leaving the liquid mixture still, the oil phase was fractionated. The target substance was crystallized from the oil phase, and the precipitate was recovered to obtain an imidazole compound (Compound 1) having the above structure.

[Formula 40]

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

[Synthesis method of compound 2]

As Compound 2, an imidazole compound having the following structure was synthesized.

[Formula 41]

Specifically, an imidazole compound (Compound 2) having the above structure was obtained in the same manner as in the synthesis method of Compound 1, except that the raw material compound was changed to a cinnamic acid derivative having the structure of the following formula.

[Formula 42]

<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), A negative photosensitive resin composition having a solid content concentration of 15% by mass was prepared.

· Alkali-soluble resin

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

· Photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA)...65 parts by mass

・Photopolymerization initiator

"OXE-02" (trade name: manufactured by BASF)...15 parts by mass

The compound represented by the above formula (1)

1 part by mass of the above compound

· Colorant

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

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

First, in a 500 ml four-neck flask, bisphenol fluorene type epoxy resin (epoxy equivalent 235) 235 g, tetramethylammonium chloride 110 mg, 2,6-di-tert-butyl-4-methylphenol 100 mg, and acrylic acid 72.0 g was injected and heated and dissolved at 90 to 100°C while blowing air into it at a rate of 25 ml/min. Next, the temperature of the solution was gradually raised as it was in a cloudy state, and heated to 120°C to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH/g. Twelve hours were required until the acid value reached the target value. And it cooled to room temperature, and the bisphenol fluorene type|mold epoxy acrylate represented by the following formula (a-4) which was colorless and transparent and was solid was obtained.

[Formula 43]

Next, after adding and dissolving 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. Then, the temperature was gradually raised and reacted at 110 to 115°C for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, it was made to react at 90 degreeC for 6 hours, and resin (A-1) was obtained. Disappearance of the acid anhydride group was confirmed by an IR spectrum.

In addition, this resin (A-1) corresponds to the compound represented by the said 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 Compound 2 and Comparative Compounds 1 to 3 were used instead of Compound 1, or Compound 1 was not used.

[evaluation]

The negative photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 and 4 were coated on a glass substrate (100 mm × 100 mm) using a spin coater, prebaked at 90 ° C. for 120 seconds, and the film thickness A coating film of 1.0 µm was formed. Next, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 µm, and the coating film was irradiated with ultraviolet rays through a negative mask having a 20 µm line pattern. The exposure amount was set to four stages of 20, 40, 60, and 120 mJ/cm 2 . A line pattern was formed by post-baking the coated film after exposure at 230 degreeC for 30 minutes after image development for 40 second with the 26 degreeC 0.04 mass % KOH aqueous solution.

Similarly, the coating film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative mask in which line patterns of 2, 5, 10, and 20 μm were formed. The exposure amount was 10 mJ/cm 2 . A line pattern was formed by post-baking the coated film after exposure at 230 degreeC for 30 minutes after image development for 40 second with 26 degreeC 0.04 mass % KOH aqueous solution.

About the formed line pattern, the OD value per 1 micrometer of film thickness was measured using the OD measuring apparatus D-200II (made by Gretac Macbeth).

In addition, the line pattern was observed with an optical microscope, and pattern straightness was evaluated. Pattern straightness was evaluated as "good" when there was no jaggedness at the edge of the line, and "poor" when there was jaggedness.

In addition, the line pattern was observed with an optical microscope, and pattern adhesion was evaluated. Pattern adhesion was evaluated as "Good" when a line pattern was formed without peeling from the substrate, and "None" when peeled from the substrate and no line pattern was formed.

In addition, 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 can be seen from Tables 1 and 2, when the negative photosensitive resin compositions of Examples 1 and 2 containing compound 1 or 2 represented by the formula (1) were used, even at a low exposure amount of 20 mJ/cm 2 , A line pattern with excellent straightness could be formed. Also, even at a low exposure amount of 10 mJ/cm 2 , a line pattern of 2 μm adhered to the substrate. Further, when the negative photosensitive resin compositions of Examples 1 and 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, as can be seen from Tables 3 and 4, pattern straightness and pattern adhesiveness were similar to those of Examples 1 to 2. inferior, and good micropatterning properties were not obtained.

In particular, Comparative Compound 2 contained in the negative photosensitive resin composition of Comparative Example 2 is an amine-based silane coupling agent known as an adhesion enhancer, but at a low exposure dose of 10 mJ/cm 2 , even a 20 μm line pattern adheres to the substrate. It didn't work.

In Comparative Compound 3 contained in the photosensitive resin composition of Comparative Example 3, a hydroxyl group was bonded to the ortho position of the benzene ring, but only a line pattern with poor straightness could be formed at a light exposure amount as low as 20 mJ/cm 2 . Further, at a low exposure amount of 10 mJ/cm 2 , only a line pattern of 10 μm or more was 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), 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)...66 parts by mass

· Photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA)...33 parts by mass

・Photopolymerization initiator

"OXE-02" (trade name: manufactured by BASF) 2 parts by mass

The compound represented by the above formula (1)

1 part 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 for using Compound 2 and Comparative Compounds 1 to 3 instead of Compound 1, respectively.

[evaluation]

The negative photosensitive resin compositions of Examples 3 and 4 and Comparative Examples 5 and 7 were coated on 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 was formed. Next, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 µm, and the coating film was irradiated with ultraviolet rays through a negative mask having a 20 µm line pattern. The exposure amount was set to 4 stages of 20, 40, 60, and 120 mJ/cm 2 . A line pattern was formed by post-baking the coated film after exposure at 230 degreeC for 30 minutes after image development for 40 second with 26 degreeC 0.04 mass % KOH aqueous solution.

Similarly, the coating film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative mask in which a line pattern of 5, 10, and 20 μm was formed. The exposure amount was 20 mJ/cm 2 . A line pattern was formed by post-baking the coated film after exposure at 230 degreeC for 30 minutes after image development for 40 second with 26 degreeC 0.04 mass % KOH aqueous solution.

The formed line patterns were observed with an optical microscope, and pattern straightness was evaluated. Pattern straightness was evaluated as "good" when there was no jaggedness at the edge of the line, and "poor" when there was jaggedness.

In addition, the line pattern was observed with an optical microscope, and pattern adhesion was evaluated. Pattern adhesion was evaluated as "Good" when a line pattern was formed without peeling from the substrate, and "None" when peeled from the substrate and no line pattern was formed.

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

A result is shown to following Tables 5-8.

As can be seen from Tables 5 and 6, when the negative photosensitive resin compositions of Examples 3 and 4 containing the compound 1 or 2 represented by the formula (1) were used, even at a low exposure amount of 20 mJ/cm 2 , A line pattern with excellent straightness could be formed. Further, even at a low exposure amount of 20 mJ/cm 2 , a line pattern of 5 μm adhered to the substrate. Further, when the negative photosensitive resin compositions of Examples 3 and 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, as can be seen from Tables 7 and 8, both the pattern straightness and the pattern adhesion were higher than those of Examples 3 to 4. It was inferior, and good micropatterning properties were not obtained.

In particular, Comparative Compound 2 contained in the negative photosensitive resin composition of Comparative Example 6 is an amine-based silane coupling agent known as an adhesion enhancer, but at a low exposure amount of 20 mJ/cm 2 , even a 20 μm line pattern adheres to the substrate. It didn't work.

In Comparative Compound 3 contained in the negative photosensitive resin composition of Comparative Example 7, a hydroxyl group was bonded to the ortho position of the benzene ring, but only a line pattern with poor straightness could be formed at a light exposure amount as low as 20 mJ/cm 2 . Further, at a low exposure amount of 20 mJ/cm 2 , only a line pattern of 10 μm or 20 μm or more was adhered to the substrate.

[Example 5]

50 parts by mass of polyp-hydroxystyrene (mass average molecular weight 2500), 50 parts by mass of a copolymer of p-hydroxystyrene/styrene = 85/15 (molar ratio) (mass average molecular weight 2500), and Nigalak MW, which is a melamine resin 15 parts by mass of -100LM (manufactured by Sanwa Chemical Co., Ltd.) was dissolved in 247 parts by mass of propylene glycol monomethyl ether acetate, and 15 parts by mass of α-(methylsulfonyloxyimino)-1-phenylacetonitrile as a photoacid generator and 2 parts by mass were dissolved therein. 3.0 parts by mass of 3,3',4,4',5'-hexahydroxybenzophenone was dissolved, and further, the compound 1 was added so as to be 3% by mass in the solid content, thereby preparing a negative photosensitive resin composition.

[Example 6]

Except having added the said compound 1 so that it might become 8 mass % in solid content, it carried out similarly to Example 5, and prepared the negative photosensitive resin composition.

[Example 7]

Except having used the said compound 2 instead of the said compound 1, it carried out similarly to Example 5, and prepared the negative photosensitive resin composition.

[Example 8]

Except having added the said compound 2 so that it might become 8 mass % in solid content, it carried out similarly to Example 7, and prepared the negative photosensitive resin composition.

[Comparative Example 8]

Except not adding the said compound 1, it carried out similarly to Example 5, and prepared the negative photosensitive resin composition.

[evaluation]

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

The formed line pattern was observed with a scanning electron microscope (SEM), and pattern adhesion was evaluated. Pattern adhesion was evaluated as "good" when the line was completely reproduced, and "poor" when all peeling, partial peeling, or defect occurred.

In addition, the line pattern was observed with a scanning electron microscope (SEM), and the pattern shape was evaluated. Regarding the pattern shape, a rectangular pattern perpendicular to the substrate was evaluated as "good", and a phenomenon of tapering toward the end of the upper part of the pattern or wavy phenomena on the side surface was evaluated as "poor".

In addition, 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 can be seen from Tables 9 and 10, in the case of using the negative photosensitive resin compositions of Examples 5 to 8 to which compound 1 or 2 represented by the formula (1) was added, even at a low exposure amount of 100 mJ/cm 2 , A line pattern of 0.55 μm adhered to the substrate, and the pattern shape was 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 to which the compound represented by the formula (1) was not added was used, both pattern adhesion and pattern shape were inferior to those of Examples 5 to 8, and good micropatterning characteristics were obtained. did not lose

[Example 9]

35.0 g of the photosensitive polyimide 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 inlet tube to dissolve them. Then, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole 2.0 g (0.03 mmol), 2-mercaptobenzoxazole 1.0 g (0.66 m mol), and 0.2 g (0.06 mmol) of ethyl michler's ketone as a photosensitizer and 7.0 g (3.1 mmol) of 1,6-hexanediol diacrylate as an addition polymerizable compound were added, and further the compound 1 was added. It added so that it might become 3 mass % in solid content, and after stirring and dissolving under room temperature for one day, filter filtration was carried out and the negative photosensitive resin composition was prepared.

The synthesis method of the photosensitive polyimide precursor is as follows.

To a stirred solution of 15.27 g (0.070 mol) of pyromellitic dianhydride in 100 ml of dry N-methylpyrrolidone under dry nitrogen was added 1.30 g (0.010 mol) of 2-hydroxyethylmethacrylate. The solution was stirred at room temperature for 1 hour and at 35°C for 1 hour, then cooled to room temperature. This reaction solution was mixed with 8.49 g (0.040 mol) of 3,3'-dimethyl-4,4'-diaminobiphenyl and 0.25 g (0.001 mol) of 1,3- It was added dropwise over 1 hour to a stirred solution of bis(3-aminopropyl)tetramethyldisiloxane, and stirred overnight at room temperature. 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 over 30 minutes while stirring. To this 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 at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which impurities were removed by suction filtration was treated with 2.0 liters of ion-exchanged water while vigorously stirring. The precipitated solid was washed with ion-exchanged water, further washed with methanol, dried by suction on a filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by mass to obtain a photosensitive polyimide precursor.

[Example 10]

Except having added the said compound 1 so that it might become 8 mass % in solid content, it carried out similarly to Example 9, and prepared the negative photosensitive resin composition.

[Example 11]

Except having used the said compound 2 instead of the said compound 1, it carried out similarly to Example 9, and prepared the negative photosensitive resin composition.

[Example 12]

Except having added the said compound 2 so that it might become 8 mass % in solid content, it carried out similarly to Example 11, and prepared the negative photosensitive resin composition.

[Comparative Example 9]

Except not adding the said compound 1, it carried out similarly to Example 9, and prepared the negative photosensitive resin composition.

[evaluation]

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

The formed line pattern was observed with a scanning electron microscope (SEM), and pattern adhesion was evaluated. Pattern adhesion was evaluated as "good" when the line was completely reproduced, and "poor" when all peeling, partial peeling, or defect occurred.

In addition, the line pattern was observed with a scanning electron microscope (SEM), and the pattern shape was evaluated. Regarding the pattern shape, a rectangular pattern perpendicular to the substrate was evaluated as "good", and a phenomenon in which the top of the pattern was tapered toward the end or a phenomenon in which wavy lines occurred on the side surface was evaluated as "poor".

In addition, 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, in the case of using the negative photosensitive resin compositions of Examples 9 to 12 to which compound 1 or 2 represented by the formula (1) was added, a 6.0 μm line pattern adhered to the substrate. and the pattern shape was 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 to which the compound represented by the formula (1) was not added was used, both pattern adhesion and pattern shape were inferior to those of Examples 9 to 12, and good micropatterning characteristics were obtained. not obtained

[Example 13]

A negative photosensitive resin composition was prepared by mixing 100 parts by mass of the polyimide precursor, 15 parts by mass of the compound 1, and 843 parts by mass of N-methyl-2-pyrrolidone.

The synthesis method of the polyimide precursor is as follows.

10.0 g (50 mmol) of di(4-aminophenyl)ether was put into a 300 ml three-necked flask, dissolved in 105.4 ml of dehydrated N,N-dimethylacetamide (DMAc), and placed in an ice bath under a nitrogen stream. was stirred while cooling. Thereto, 14.7 g (50 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added little by little, and after the addition was completed, the solution was stirred in an ice bath for 5 hours, and the solution was dehydrated. It was reprecipitated with diethyl ether, and the precipitate was dried at room temperature under reduced pressure for 17 hours to quantitatively obtain a polyamic acid (polyimide precursor) having a mass average molecular weight of 10000 as a white solid.

[Example 14, Comparative Examples 10 to 11]

A negative photosensitive resin composition was prepared in the same manner as in Example 13, except that Compound 2 and Comparative Compounds 2 and 3 were used instead of Compound 1, respectively.

[evaluation]

The negative photosensitive resin compositions of Examples 13 and 14 and Comparative Examples 10 and 11 were spin-coated on a chrome-plated glass substrate to a final film thickness of 4 μm, and dried on a hot plate at 80 ° C. for 10 minutes to obtain a coated film. . Next, using a mirror projection aligner (product name: MPA-600FA, manufactured by Canon Inc.), the coating film was irradiated with ultraviolet rays through a negative mask in which a 20 µm line pattern was formed. The exposure amount was 200, 300, 400 and 500 mJ/cm 2 in five stages. The coated film after exposure was heated on a hot plate at 140 ° C. for 10 minutes (heating after exposure), and then immersed in a developing solution in which a 2.38% by mass aqueous solution of tetramethylammonium hydroxide and isopropanol were mixed at a volume ratio of 9: 1 to develop, A line pattern was formed by post-baking at 350 degreeC for 1 hour and imidating.

The formed line pattern was observed with a scanning electron microscope (SEM), and the pattern formability was evaluated. Pattern formation was evaluated as "good" when a line was completely reproduced, and "poor" when all peeling or partial peeling or chipping occurred.

In addition, the line pattern was observed with an optical microscope, and pattern straightness was evaluated. Pattern straightness was evaluated as "good" when there was no jaggedness at the edge of the line, and "poor" when there was jaggedness.

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

The results are shown in Tables 13 and 14 below.

As can be seen from Tables 13 and 14, when the negative photosensitive resin compositions of Examples 13 to 14 containing compound 1 or 2 represented by the above formula (1) were used, patterns were obtained at a low exposure amount of 200 mJ/cm 2 . It was possible to form a 20 μm line pattern with excellent shape and excellent straightness at a low exposure amount of 300 mJ/cm 2 . Further, when the negative photosensitive resin compositions of Examples 13 and 14 were used, there was no development residue.

On the other hand, when the negative photosensitive resin compositions of Comparative Examples 10 to 11 not containing the compound represented by the above formula (1) were used, both the pattern formability and the pattern straightness were inferior to those of Examples 13 to 14, resulting in a good smile. No patterning properties were obtained.

[Example 15]

A negative photosensitive resin composition was prepared by mixing 100 parts by mass of an epoxy resin (YP50EK35 (phenoxy resin), a 35% by mass methyl ethyl ketone solution, manufactured by Nippon Steel Chemical Co., Ltd.) and 10 parts by mass of the above compound 1.

[Example 16, Comparative Examples 12 to 13]

A negative photosensitive resin composition was prepared in the same manner as in Example 15, except that Compound 2 and Comparative Compounds 2 and 3 were used instead of Compound 1, respectively.

[evaluation]

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

The formed line pattern was observed with a scanning electron microscope (SEM), and the pattern formability was evaluated. Pattern formation was evaluated as "good" when a line was completely reproduced, and "poor" when all peeling or partial peeling or chipping occurred.

In addition, the line pattern was observed with an optical microscope, and pattern straightness was evaluated. Pattern straightness was evaluated as "good" when there was no jaggedness at the edge of the line, and "poor" when there was jaggedness.

In addition, 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, in the case of using the negative photosensitive resin compositions of Examples 15 to 16 containing compound 1 or 2 represented by the formula (1), 70 mJ without heating after exposure. It was possible to form a 20 μm line pattern excellent in pattern shape at a low exposure dose of /cm 2 and excellent in straightness at an exposure dose of 80 mJ/cm 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 compositions of Comparative Examples 12 to 13 not containing the compound represented by the above formula (1) were used, both the pattern formability and the pattern straightness were inferior to those of Examples 15 to 16, resulting in a good smile. No patterning properties were obtained.

[Example 17]

Each of the following components (mass part is in terms of solid content) was kneaded with a 3-roll mill to prepare a negative photosensitive resin composition.

· Epoxy group-containing polycarboxylic acid resin

Resin (F-1)...58.3 parts by mass

· Mineral generator

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

The compound represented by the above formula (1)

1 part by mass of the above compound

· Sensitizer

2-Ethyl-9,10-dimethoxyanthracene...0.4 part by mass

· Modifying ingredients

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

"Cymel300" (trade name: manufactured by Nippon Cytech, melamine resin) ... 11.7 parts by mass

· Filler

"Silbond 800EST" (trade name: manufactured by Shiraishi Calcium Co., Ltd., surface-treated spherical silica)...25.0 parts by mass

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

"SG-2000" (trade name: manufactured by Nippon Talc Co., Ltd., talc) ... 5.8 parts by mass

· additive

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

"BYK-354" (trade name: manufactured by Big Chemie, leveling agent)...1.6 parts by mass

"BYK-057" (trade name: manufactured by Big Chemie, antifoaming agent)...1.6 parts by mass

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

Epoxy resin obtained by the reaction of biphenyldimethylene-hydroxyphenylene and epichlorohydrin (manufactured by Nippon Chemical Co., Ltd., NC-3000PL, epoxy equivalent 274, softening point 57.3 ° C.) 211.2 g, dimethylolpropionic acid 72.4 g, carbitol acetate 70.9 g and 0.71 g of triphenylphosphine were charged, heated at 100°C, and reacted until the acid value of the reaction solution became 1 mgKOH/g or less. The reaction time was 24 hours. Subsequently, 0.51 g of percumyl H80 (manufactured by Nippon Oil Co., Ltd., peroxide) was injected into this reaction solution, and stirred for about 2 hours to oxidize and inactivate triphenylphosphine as a reaction catalyst. Then, 66.4 g of tetrahydrophthalic anhydride and 117.6 g of carbitol acetate were charged, and it was made to react at 95 degreeC for 4 hours, and Resin (F-1) was obtained. The acid value of Resin (F-1) was 70 mgKOH/g.

[Example 18]

Except having used the said compound 2 instead of the said compound 1, respectively, it carried out similarly to Example 17, and prepared the negative photosensitive resin composition.

[Comparative Example 14]

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

[Comparative Example 15]

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

[Comparative Example 16]

The blending amount of Resin (F-1) was 57.0 parts by mass, the blending amount of "PCI-220" was 4.1 parts by mass, the blending amount of 2-ethyl-9,10-dimethoxyanthracene was 2.1 parts by mass, and the blending amount of "Cymel300" was 4.1 parts by mass. A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 14 except that the blending amount was 11.4 parts by mass.

[evaluation]

The negative photosensitive resin compositions of Examples 17 to 18 and Comparative Examples 14 to 16 were screen-printed using a 100-mesh stainless steel screen to a thickness of 25 μm, and the entire surface was patterned on a copper-clad laminate. It applied, and the coating film was dried for 30 minutes with an 80 degreeC hot air dryer. Then, a quartz mask having line patterns of 40 μm, 45 μm, 50 μm, and 60 μm was formed in close contact with the coating film, and using an ultraviolet exposure device (product name: EXM-1066, manufactured by Oak Manufacturing Co., Ltd.), ultraviolet rays were applied to the coating film. was investigated. The exposure amount was 500 mJ/cm 2 . Subsequently, after performing a post-exposure bake treatment with a hot air dryer, it was developed with a 25°C 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2 kg/cm 2 , and the unexposed portion was dissolved and removed. Thereafter, heat curing was performed for 60 minutes with a 150°C hot air dryer.

The formed line pattern was observed with a scanning electron microscope (SEM), and pattern adhesion was evaluated. Pattern adhesion was evaluated as "good" when the line was completely reproduced, and "poor" when all peeling, partial peeling, or defect occurred.

In addition, the line pattern was observed with a scanning electron microscope (SEM), and the pattern shape was evaluated. The pattern shape was rectangular, and those with no penetration by taper or development were evaluated as "good", and those with penetration by taper or development were evaluated as "poor".

In addition, 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 compositions of Examples 17 to 18 containing compound 1 or 2 represented by the formula (1) were used, a 40 μm line pattern closely adhered to the substrate. and the pattern shape was 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 in which the compound represented by the formula (1) was not incorporated were used, both pattern adhesion and pattern shape were inferior to those of Examples 17 to 18, and good micropatterning characteristics were obtained. this was not obtained

[Example 19]

Each of the following components was mixed, dissolved in a mixed solvent of methylethyldiglycol/propylene glycol monomethyl ether acetate = 40/60 (mass ratio), and a negative photosensitive resin composition having a solid content concentration of 15% by mass was prepared.

· Alkali-soluble resin

Resin (A-3) (4-oxatetracyclo-[6.2.1.0 ^2,7 0 ^3,5 ]undecanyl(meth)acrylate/methacrylic acid/tricyclodecylmethacrylate = 72/18/10 ( mass ratio), mass average molecular weight 14000) ... 66 parts by mass

· Photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA)...34 parts by mass

・Photopolymerization initiator

Initiator 1 (oxime ester compound 1 represented by the following formula synthesized by Synthesis Examples 1 to 3 below)...6 parts by mass

[Formula 44]

The compound represented by the above formula (1)

1 part by mass of the above compound

· additive

Carboxybenzotriazole ... 1 part by mass

[Synthesis Example 1]

(Synthesis of 9,9-di-n-propylfluorene)

6.64 g (40 mmol) of fluorene was dissolved in 27 ml of tetrahydrofuran (THF). To the obtained solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 ml of an aqueous sodium hydroxide solution having a concentration of 50% by mass were gradually added under a nitrogen atmosphere. The obtained mixture was stirred at 80°C for 3 hours to react. After adding 33 g of ethyl acetate and 33 g of water to the mixture after reaction, it separated into an organic layer and an aqueous layer. After dehydrating the obtained organic layer with anhydrous sodium sulfate, the solvent was removed from the organic layer using a rotary evaporator to obtain 8.32 g of 9,9-di-n-propylfluorene (83% yield).

[Synthesis Example 2]

4.10 g (16.37 mmol) of 9,9-di-n-propylfluorene and 3.04 g (18.00 mmol) of (2-methylphenyl)acetic acid chloride, in the presence of 2.62 g of aluminum chloride, dichloromethane solvent, 50 ml Inside, it was made to react under ice-cooling for 1 hour. 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 then evaporated. The residue was purified on a silica gel column with ethyl acetate/hexane = 1/2 as an eluent to obtain 5.95 g (15.55 mmol) of 2-(2-methylphenyl)acetyl-9,9-di-n-propylfluorene. 2-(2-methylphenyl)acetyl-9,9-di-n-propylfluorene 5.95 g (15.55 mmol) and concentrated hydrochloric acid 1.60 g (15.55 mmol), isobutyl nitrite 2.42 g (23.33 mmol) In the presence of 25 ml of dimethylformamide solvent, it was made to react for 3 hours under ice-cooling. The reaction solution was evaporated, ethyl acetate was added to the residue, washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to obtain 2-[2-methylphenyl(hydroxyimino)acetyl of the following structure 4.80 g (11.67 mmol) of ]-9,9-di-n-propylfluorene was obtained.

[Formula 45]

The measurement results of ¹ H-NMR of 2-[2-methylphenyl(hydroxyimino)acetyl]-9,9-di-n-propylfluorene were as follows.

[Synthesis Example 3]

4.80 g (11.67 mmol) of 2-[2-methylphenyl(hydroxyimino)acetyl]-9,9-di-n-propylfluorene, 1.43 g (13.42 mmol) of acetic anhydride, and 1.36 g of triethylamine (13.42 mmol) and 45.00 ml of dimethylformamide solvent were mixed, and it stirred at 35 degreeC for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate, and then evaporated. The residue was purified by a silica gel column with an eluent of ethyl acetate/hexane = 2/1 to obtain 4.76 g (10.50 mmol, 72% yield) of an oxime ester compound 1.

The measurement results of ¹ H-NMR of the oxime ester compound 1 were as follows.

[evaluation]

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 thickness of 1.0 µm. Next, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 µm, and the coating film was irradiated with ultraviolet rays through a negative mask having a 20 µm line pattern. The exposure amount was set to four stages of 20, 40, 60, and 120 mJ/cm 2 . The line pattern was formed by post-baking the coated film after exposure at 230 degreeC for 30 minutes after image development for 40 second with the 23 degreeC 2.38 mass % TMAH aqueous solution.

Similarly, the coated film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative mask in which line patterns of 5, 10, and 20 μm were formed. The exposure amount was 20 mJ/cm 2 . The line pattern was formed by post-baking the coated film after exposure at 230 degreeC for 30 minutes after image development for 40 second with the 23 degreeC 2.38 mass % TMAH aqueous solution.

The formed line patterns were observed with an optical microscope, and pattern straightness was evaluated. Pattern straightness was evaluated as "good" when there was no jaggedness on the edge of the line, and "poor" when there was jaggedness.

Moreover, the line pattern was observed with an optical microscope, and pattern adhesiveness was evaluated. Pattern adhesion was evaluated as "Good" when a pattern was formed without peeling from the substrate, and "None" when peeled from the substrate and no line pattern was formed.

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

A result is shown to Tables 19-20 below.

As can be seen from Table 19, when the negative photosensitive resin composition of Example 19 containing the compound 1 represented by the above formula (1) was used on a copper substrate, even at a low exposure amount of 20 mJ/cm 2 , linearity This excellent line pattern could be formed. Also, even at a low exposure amount of 20 mJ/cm 2 , a line pattern of 5 μm adhered to the substrate. Further, when the negative photosensitive resin composition of Example 19 was used, there was no development residue.

Claims (11)

A negative photosensitive resin composition containing a compound represented by the following formula (1).

(In 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, R ⁴ is each independently a halogen atom or a hydroxyl group , mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, or an organic group, and n is an integer of 0 to 3 .) According to claim 1,
Furthermore, a negative photosensitive resin composition containing 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. According to claim 1,
Furthermore, a negative photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator, and an organic solvent. According to claim 3,
A negative photosensitive resin composition further containing a photopolymerizable monomer. According to claim 3,
A negative photosensitive resin composition further containing a colorant. According to claim 5,
The negative photosensitive resin composition in which the said coloring agent is a light-shielding agent. A pattern formation method comprising forming a coated film or molded body using the negative photosensitive resin composition according to any one of claims 1 to 6, irradiating the coated film or molded body with electromagnetic waves in a predetermined pattern, and developing the molded body. . A cured film formed using the negative photosensitive resin composition according to any one of claims 1 to 4. An insulating film formed using the negative photosensitive resin composition according to any one of claims 1 to 4. A color filter formed using the negative photosensitive resin composition according to claim 5 or 6. A cured film formed using the negative photosensitive resin composition according to any one of claims 1 to 4, an insulating film formed using the negative photosensitive resin composition according to any one of claims 1 to 4, or A display device provided with a color filter formed using the negative photosensitive resin composition according to claim 5 or 6.