TWI579645B - A photosensitive resin composition for forming an insulating film, an insulating film, and an insulating film - Google Patents

Description

Photosensitive resin composition for forming an insulating film, insulating film, and method for forming insulating film

The present invention relates to a photosensitive resin composition for forming an insulating film, an insulating film formed of the photosensitive resin composition for forming the insulating film, and a method for forming an insulating film using the photosensitive resin composition for forming the insulating film.

In an electronic component such as a liquid crystal display element, an integrated circuit element, or a solid-state image sensing device, an insulating film or the like is formed between the wirings in a layered arrangement. This insulating film is formed of various materials such as an inorganic film or an organic film, and when it is an organic film, a thermosetting resin composition or a photosensitive resin composition is often used.

As a photosensitive resin composition used for forming such an insulating film, a monomer containing an unsaturated double bond, a monomer containing a carboxylic acid and an unsaturated double bond, and an allyl group-containing monomer are known. A copolymer of a monomer having a specific structure, which comprises an alkali-soluble resin having a molecular weight distribution (Mw/Mn) of 1.0 to 3.5, a polymerizable compound having an ethylenically unsaturated bond, and a photosensitive resin composition with a photoinitiator (Refer to Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-012602

However, the photosensitive resin composition described in Patent Document 1 has a problem that the insulating film having good insulating properties can be formed with a narrow exposure margin and a low degree of freedom in processing conditions when forming an insulating film. In addition, in the processing steps of the processing step or the electronic component including the insulating film, for example, the insulating film is exposed to various kinds of chemical liquids such as a resist stripping liquid, and therefore, chemical resistance is required to be excellent. However, the photosensitive resin element composition described in Patent Document 1 is not always sufficient for durability of a chemical liquid such as a photoresist peeling liquid.

In view of the above-described problems, the present invention has an object of providing a photosensitive resin composition for forming an insulating film, which is capable of forming an insulating film having excellent insulating properties and chemical resistance, and has a wide exposure margin when forming a pattern of an insulating film. . Moreover, the present invention has an object of providing an insulating film formed using the photosensitive resin composition for forming an insulating film and a method of forming an insulating film using the photosensitive resin composition for forming an insulating film.

The present inventors have made extensive efforts to solve the above problems. Research. As a result, it has been found that a compound having a specific structure is used in a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and the compound is contained therein. The present invention can be solved by providing a resin having a specific amount of an epoxy group-containing unsaturated compound as the (A) alkali-soluble resin. Specifically, the present invention provides the following.

The first aspect of the present invention is a photosensitive resin composition for forming an insulating film, which comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) The compound represented by the following formula (1), wherein the (A) alkali-soluble resin contains a copolymer of a constituent unit derived from an epoxy group-containing unsaturated compound, and the (A) alkali-soluble resin contains the epoxy group. The ratio of the constituent units derived from the unsaturated compound is 20 to 60% by mass;

(Wherein, R ¹ is and R ² each independently represent a hydrogen atom lines or an organic group, provided, R ¹ and R ² represents a system of at least one organic group, R ¹ and R ² may be bonded via for other to form a cyclic structure And may also contain a bond of a hetero atom; R ³ represents a single bond or an organic group; and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, and a nitrate Base, nitroso, sulfinate, sulfonate, sulfonate, phosphino, phosphinyl, phosphonium, phosphonato or organic, R ⁶ , R ⁷ , R ⁸ and R ^{The 9} series independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfonic acid group, a sulfonate group, a phosphino group, and an oxygen group. a phosphino group, a phosphonium group, a phosphonate group, an amine group, an ammonium group or an organic group. However, R ⁶ and R ^{7 are} not a hydroxyl group, and R ⁶ , R ⁷ , R ⁸ and R ⁹ may be both The bond forms a ring structure and may also contain a bond of a hetero atom; R ¹⁰ represents a hydrogen atom or an organic group).

The second aspect of the present invention is an insulating film formed using the photosensitive resin composition for forming an insulating film of the first aspect.

A third aspect of the present invention provides a method for forming an insulating film, comprising: coating a photosensitive resin composition for forming an insulating film of a first aspect on a substrate; and forming a photosensitive resin layer; The pattern of the specified insulating film is an exposure step of exposing the photosensitive resin layer; and a developing step of developing a pattern of the exposed photosensitive resin layer to form an insulating film.

According to the present invention, it is possible to provide a photosensitive resin composition for forming an insulating film which can form an insulating film having excellent insulating properties and chemical resistance, and has a wide exposure margin when forming a pattern of an insulating film. Moreover, according to the present invention, it is possible to provide an insulating film formed using the photosensitive resin composition for forming an insulating film, and a photosensitive resin composition for forming the insulating film. A method of forming an insulating film.

Photosensitive resin composition for forming an insulating film ≪

The photosensitive resin composition for forming an insulating film of the present invention (hereinafter also referred to as "photosensitive resin composition") contains at least (A) an alkali-soluble resin (hereinafter also referred to as "(A) component"), (B) a photopolymerizable monomer (hereinafter also referred to as "(B) component"), (C) a photopolymerization initiator (hereinafter also referred to as "(C) component"), and (D) A compound represented by the formula (1) (hereinafter also referred to as "(D) component"). Hereinafter, each component contained in the photosensitive resin composition for forming an insulating film of the present invention will be described.

<(A) alkali soluble resin>

The alkali-soluble resin is a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and a resin film having a thickness of 1 μm is formed on a substrate, and then impregnated with a KOH aqueous solution having a concentration of 0.05% by mass. At 1 minute, the film thickness of 0.01 μm or more can be dissolved.

(A) The alkali-soluble resin is a copolymer comprising a constituent unit derived from an unsaturated compound containing an epoxy group. In the alkali-soluble resin, the ratio of the constituent unit of the epoxy group-containing unsaturated compound is 20 to 60% by mass, preferably 20 to 40% by mass. By using such a ratio, a constituent unit containing an unsaturated compound containing an epoxy group is used. The (A) alkali-soluble resin can easily form an insulating film excellent in insulating properties with a photosensitive resin composition.

The resin used as the component (A) is as long as it contains The constituent unit of the epoxy group-containing unsaturated compound is not particularly limited, and the alkali-soluble resin used in various photosensitive resin compositions can be appropriately selected and used. The resin which is suitable as the component (A) is exemplified by a copolymer which polymerizes at least (a1) unsaturated carboxylic acid and (a2) epoxy group-containing unsaturated compound from the viewpoint of easily obtaining an insulating film excellent in chemical resistance. (A1).

(a1) an unsaturated carboxylic acid, for example, (meth) propyl a monocarboxylic acid such as an acid or a crotonic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; or a carboxylic acid anhydride; and the like. Among these, (meth)acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, availability of alkali solubility of the resin, ease of handling, and the like. These (a1) unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

(a2) an epoxy group-containing unsaturated compound, which can be exemplified Such as (a2-I) an alicyclic epoxy group-containing unsaturated compound, and (a2-II) an alicyclic epoxy group-free unsaturated compound, and (a2-I) an alicyclic epoxy group The unsaturated compound is preferred.

(a2-I) among the unsaturated compounds containing an alicyclic epoxy group, The alicyclic group constituting the alicyclic epoxy group may be a single ring or a polycyclic ring. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a thiol group, an isoindole group, a tricyclic fluorenyl group, a tricyclic fluorenyl group, and a tetracyclic decyl group. (a2-I) alicyclic epoxy group The unsaturated compound may be used alone or in combination of two or more.

Specifically, the (a2-I) unsaturated ring-containing epoxy group is unsaturated. The compound may, for example, be a compound represented by the following formulas (a2-1) to (a2-16). Among these, in order to make the developability moderate, compounds represented by the following formulas (a2-1) to (a2-6) are preferred, and the following formulas (a2-1) to (a2-4) are shown. The compound is better.

In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10; . R ^{12 is} a linear or branched alkyl group such as methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene or hexamethylene. R ^{13 is,} for example, methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene, hexamethylene, phenyl, cyclohexene, -CH ₂ - Ph-CH ₂ - (Ph represents a phenylene group) is preferred.

(a2-II) an epoxy group-containing unsaturated group containing no alicyclic group And a compound, for example, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3, 4-epoxy butyl (meth) acrylate, 6, 7- Epoxyalkyl (meth)acrylates such as epoxyheptyl (meth) acrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl An α-alkyl acrylate epoxyalkyl ester such as glycidyl acrylate or α-ethyl acrylate 6,7-epoxyheptyl ester; and the like. Among these, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and 6, 7-ring are observed from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like. Oxyheptyl (meth) acrylate is preferred. (a2-II) The epoxy group-containing unsaturated compound which does not contain an alicyclic group may be used individually or in combination of 2 or more types.

The copolymer (A1) may be the above (a1) unsaturated carboxylic acid and (a2) an epoxy group-containing unsaturated compound, and (a3) an epoxy group-containing unsaturated group containing an alicyclic group. Aggregated by.

(a3) The unsaturated compound containing an alicyclic group is not particularly limited as long as it contains an alicyclic group-containing unsaturated compound. The alicyclic group may be a single ring or a polycyclic ring. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, examples of the polycyclic alicyclic group include adamantyl group, norbornyl group, isodecyl group, tricyclodecyl group, tricyclodecyl group, tetracyclododecyl group and the like. These (a3) unsaturated compounds containing an alicyclic group may be used individually or in combination of 2 or more types.

Specifically, (a3) an unsaturated compound containing an alicyclic group may, for example, be a compound represented by the following formulas (a3-1) to (a3-7). Among these, a photosensitive resin composition having good developability is easily obtained. In view of the above, the compounds represented by the following formulas (a3-3) to (a3-8) are preferred, and the compounds represented by the following formulas (a3-3) and (a3-4) are more preferable.

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^{22 is} a single bond, a linear or branched alkyl group, such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, pentamethylene, hexamethylene It is better. R ²³ is preferably, for example, a methyl group or an ethyl group.

The copolymer (A1) may be further polymerized with other compounds than the above. Examples of such other compounds include (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These compounds may be used alone or in combination of two or more.

(meth) acrylates, for example, methyl (A) Linear or branched such as acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, t-octyl (meth) acrylate Alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethyl hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, three Hydrocarbylmethylpropane mono(meth)acrylate, benzyl (meth) acrylate, mercapto (meth) acrylate; and the like.

(Methyl) acrylamides, for example, (methyl) Acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl ( Methyl) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and the like.

The allyl compound may, for example, be allyl acetate or Allyl acrylate, allyl octylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetate, allyl lactate, etc. Base esters; allyloxyethanol; and the like.

Vinyl ethers, for example, hexyl vinyl ether, octane Vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-Dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethyl An alkyl vinyl ether such as aminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether Vinyl chlorophenyl ether, a vinyl aryl ether such as vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl benzamidine imine or the like;

Vinyl esters, for example, vinyl butyrate, B Alkenyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetic acid Ester, vinyl methoxy acetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetonitrile acetate, vinyl lactate, vinyl-β-phenyl butyl An acid ester, a vinyl benzoate, a vinyl salicylate, a vinyl chlorobenzoate, a vinyl tetrachlorobenzoate, a vinyl naphthoate or the like.

Styrene, for example, styrene; methyl benzene Alkene, dimethyl styrene, trimethylstyrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, Alkyl styrene such as benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl styrene; methoxy styrene, 4-methyl Alkoxystyrene such as oxy-3-methylstyrene or dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromobenzene Halogenated styrene such as ethylene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene ;Wait.

The above (a1) is derived from a constituent unit of an unsaturated carboxylic acid. The proportion of the polymer (A1) is preferably from 1 to 25% by mass, more preferably from 8 to 16% by mass. Further, the above (a3) is derived from an unsaturated group containing an alicyclic group. The proportion of the constituent unit of the compound in the copolymer (A1) is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

Mass average molecular weight of copolymer (A1) (Mw: gel The measurement value of osmotic chromatography (GPC) in terms of styrene, which is the same in the present specification, is preferably from 2,000 to 200,000, more preferably from 5,000 to 30,000. According to the above range, there is a tendency that the film formation ability of the photosensitive resin composition and the balance of developability after exposure tend to be obtained.

The copolymer (A1) can be produced by a known free radical polymerization method. Made. In other words, each compound can be produced by dissolving a known radical polymerization initiator in a polymerization solvent, heating and stirring.

Further, (A) an alkali-soluble resin can be suitably used to contain a total of a resin of the polymer (A2), wherein the copolymer (A2) has at least the constituent unit derived from the (a1) unsaturated carboxylic acid, the constituent unit derived from the (a2) epoxy group-containing unsaturated compound, and the The constituent unit of the portion where the photopolymerizable monomer is polymerized as described later (B). When the alkali-soluble resin (A) contains the copolymer (A2), the adhesion of the photosensitive resin composition to the substrate and the breaking strength of the photosensitive resin composition after curing can be improved.

Copolymer (A2), also in copolymer (A1) Other compounds described are: (meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, etc., and further copolymerized.

Containing a structure that can be polymerized with (B) photopolymerizable monomer a unit that contains ethylenically unsaturated groups as photopolymerizable with (B) The site of the sex monomer is preferred. The copolymer (A2) may be a part of the epoxy group in the copolymer of the constituent unit derived from the (a1) unsaturated carboxylic acid and the (a2) epoxy group-containing unsaturated compound. It is prepared by reacting with (a1) an unsaturated carboxylic acid.

The mass average molecular weight of the copolymer (A2) is 2000~50000 is better, and 5000~30000 is better. According to the above range, there is a tendency that the film formation ability of the photosensitive resin composition and the balance of developability after exposure tend to be obtained.

(A) content of alkali-soluble resin, for photosensitive resin group The solid content of the product is preferably 30 to 90% by mass, more preferably 45 to 75% by mass. According to the above range, there is a tendency to easily obtain a balance of developability.

<(B) Photorefractive monomer>

In the (B) photopolymerizable monomer contained in the photosensitive resin composition for forming an insulating film of the present invention, a monomer containing an ethylenically unsaturated group can be preferably used. Among the monomers containing an ethylenically unsaturated group, there are a monofunctional monomer and a polyfunctional monomer.

Monofunctional monomer, for example, (meth) propylene oxime Amine, hydrocarbon methyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) propylene oxime Amine, butoxymethoxymethyl (meth) acrylamide, N-hydrocarbylmethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, Fumaric acid, maleic acid, maleic anhydride, Iraq Kang acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propenylamine-2-methylpropane sulfonic acid, tert-butyl acrylamide sulfonic acid, methyl (meth) acrylate , ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Ester, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) Propylene oxime-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidol Base (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half of decanoic acid derivative (Meth) acrylate, etc. These monofunctional monomers may be used alone or in combination of two or more.

On the other hand, a polyfunctional monomer may, for example, be 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 , butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(methyl) Acrylate, glycerol di(meth) acrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, neopentyl Tetraol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dioxane Tetrakilenyl (meth) propylene Acid ester, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl Propane, 2-hydroxy-3-(meth)acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl Ether di(meth)acrylate, diglycidyl di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, ethyl urethane Reaction of (meth) acrylate (ie, benzylidene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth) acrylate a polyfunctional monomer such as methylene bis(meth) acrylamide, (meth) acrylamide dimethyl ether, a condensate of a polyol and N-hydrocarbylmethyl (meth) acrylamide, Or triacrylformal and the like. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers containing ethylenically unsaturated groups, In view of the adhesion between the photosensitive resin composition for forming a high insulating film and the strength after curing of the photosensitive resin composition, a polyfunctional monomer having three or more functional groups is preferable, and a polyfunctional monomer having six or more functional groups is preferable. Better.

(B) content of the component, photosensitive tree for forming an insulating film The solid content of the fat composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. According to the above range, there is a tendency to easily obtain a balance between sensitivity, developability, and resolution.

<(C) Photopolymerization initiator>

The (C) photopolymerization initiator contained in the photosensitive resin composition for forming an insulating film of the present invention is not particularly limited, and a conventionally known photopolymerization initiator can be used.

A photopolymerization initiator, specifically, for example, a 1-hydroxy ring Hexyl phenyl 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-diphenylethane-1-one, bis(4-dimethylaminophenyl)one, 2-methyl 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) )-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl], 1-(O-acetamidine) (9-ethyl-6-nitro-9H-indazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl] Ketone O-acetylindenyl, 1,2-octanedione, 1-[4-(phenylsulfanyl)-, 2-(O-benzhydrylhydrazine)], 2,4,6-tri Methyl benzhydryl diphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid Methyl ester, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino -2-isopentyl Formic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) fluorene, o- Methyl benzhydrazide, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone , thioxanthen, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, eight Methyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl fluorene, azobisisobutyronitrile, benzhydryl peroxide, cumene peroxide, 2-mercaptobenzene Imidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, two Benzene, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-di Chlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylbenzene Ethyl ketone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert- Butyl trichloroacetophenone, p-tert-butyl dichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2- Isopropyl thioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzene Formate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-( 9-Acridine)propane, p-methoxytriazine, 2,4,6-parade(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl) )-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-( Furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl ]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl) )-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4 ,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butyl Oxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl- S-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-Bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylbenzene Base-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, the use of lanthanide photopolymerization initiators, in the sense Excellent in terms of degree. Among the photopolymerization initiators of lanthanide, the most preferred one is: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl], 1-(O-ethylindenyl), (9-ethyl-6-nitro-9H-indazol-3-yl)[4-(2-methoxy-1-methylethoxy)- 2-methylphenyl]methanone O-acetamidopurine, and 1,2-octanedione, 1-[4-(phenylsulfanyl)-,2-(O-benzoguanidinopurine)] .

(C) component content, relative to the formation of insulating film The solid content of the resin composition is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass. The content of the component (C) is based on the above range, and a photosensitive resin composition capable of forming an insulating film having excellent chemical resistance can be obtained.

Further, in the component (C), a photoinitiating aid may be combined. The photoinitiating aid may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxy Base, 2-ethyl- 9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid a thiol compound such as methyl 3-mercaptopropionate, neopentyltetradecyl acetate, 3-mercaptopropionate or the like. These photoinitiating aids can be used alone or in combination of two or more.

<(D) Compound represented by formula (1)>

The photosensitive resin composition for forming an insulating film of the present invention contains a compound represented by the following formula (1). By containing this compound in the photosensitive resin composition, the exposure margin of the photosensitive resin composition can be broadened. Further, the compound represented by the formula (1) is less likely to adversely affect the sensitivity of the photosensitive resin composition or the strength of the obtained insulating film.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, and at least one of R ¹ and R ² represents an organic group.

The organic group in R ¹ and R ² may, for example, be an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain. The organic group is usually monovalent, but when it forms a cyclic structure, it can be an organic group having two or more valences.

R ¹ and R ² may form a cyclic structure for the bonding, and may also contain a bond of a hetero atom. The cyclic structure may, for example, be a heterocycloalkyl group or a heteroaryl group, or may be a condensed ring.

The bonding other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include a bond containing a hetero atom such as an oxygen atom, a nitrogen atom or a ruthenium atom. Specific examples include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, guanamine bond, urethane bond, and imine bond (-N=C (-R)-, -C(=NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinium bond, an azo bond, or the like.

From the viewpoint of heat resistance, a bond other than the hydrocarbon group in the organic group of R ¹ and R ² is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, or a guanamine bond. Junction, urethane linkage, imine linkage (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), carbonate linkage Sulfhydryl bond, sulfinyl bond is preferred.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include a halogen atom, a hydroxyl group, a thiol group, a thioether group, a cyano group, and an isocyano group. , cyanooxy, isocyanate, thiocyano, isothiocyano, decyl, decyl, alkoxy, alkoxycarbonyl, amine carbaryl, thiamine, nitro, arylene Nitro, carboxyl, carboxylate, sulfhydryl, decyloxy, sulfinate, sulfonate, sulfonate, phosphino, phosphinyl, phosphonium, phosphonate, hydroxyimino, Alkyl ether group, alkenyl ether group, alkyl sulfide group, alkyl sulfide group, aryl ether group, aryl sulfide group, amine group (-NH ₂ , -NHR, -NRR': R and R' Independently means a hydrocarbon group). The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the above substituent may be any of a linear chain, a branched chain, and a cyclic group.

a substituent other than the hydrocarbon group in the organic group of R ¹ and R ² , a halogen atom, a hydroxyl group, a thiol group, a thioether group, a cyano group, an isocyano group, a cyanooxy group, an isocyanate group, a thiocyano group, an isosulfur Cyano, decyl, decyl, alkoxy, alkoxycarbonyl, amine carbaryl, thiamine, nitro, nitroso, carboxyl, carboxylate, fluorenyl, decyloxy , sulfinic acid group, sulfonic acid group, sulfonate group, phosphino group, phosphinyl group, phosphinium group, phosphonate group, hydroxyimino group, alkyl ether group, alkenyl group, alkyl sulfide group, alkene A thioether group, an aryl ether group or an aryl sulfide group is preferred.

In the above, R ¹ and R ² are at least one of an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or a bond to each other to form a heterocycloalkyl group having 2 to 20 carbon atoms or a hetero group. Aryl is preferred. The heterocycloalkyl group may, for example, be an N-hexahydropyridyl group or a morpholinyl group. The heteroaryl group may, for example, be an imidazolyl group or a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

The organic group in R ³ may, for example, be a group in which one hydrogen atom is removed from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. The organic group may also have a substituent on the organic group. The substituent may, for example, be exemplified as R ¹ and R ² . Further, the organic group may be either linear or branched.

Among the above, R ^{3 is} preferably a single bond or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the above formula (1), R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinic acid group, or a sulfonate group. An acid group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, or an organic group.

The organic group in R ⁴ and R ⁵ may, for example, be exemplified as R ¹ and R ² . The organic group may be the same as in the case of R ¹ and R ² , and may have a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

In the above, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, and a carbon number of 7 to 16. An aryloxyalkyl group, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms containing a cyano group, an alkyl group having 1 to 10 carbon atoms and a alkoxy group having 1 to 10 carbon atoms a mercapto group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a mercapto group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group), An aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and/or an electron-withdrawing group, a benzyl group, a cyano group or a methyl group substituted by an electron-donating group and/or an electron-withdrawing group Sulfur is preferred. More preferably, both R ⁴ and R ⁵ are a hydrogen atom, or R ⁴ is a methyl group, and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, and a arylene group. Sulfonic acid group, sulfonic acid group, sulfonate group, phosphino group, phosphinyl group, phosphonium group, phosphonate group, amine group, ammonium group, or organic group.

The organic group of R ⁶ , R ⁷ , R ⁸ and R ⁹ may, for example, be exemplified as R ¹ and R ² . The organic group may be the same as in the case of R ¹ and R ² , and may have a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

Further, in the above formula (1), R ⁶ and R ^{7 are} not a hydroxyl group.

R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to each other to form a cyclic structure or may contain a bond of a hetero atom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and a condensed ring may also be used. For example, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be such that two or more of the two are bonded, and R ⁶ , R ⁷ , R ⁸ and R ⁹ together have an atom bonded to a benzene ring to form a naphthalene or an anthracene. Condensation rings such as phenanthrene and anthracene.

In the above, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and a cycloalkenyl group having 4 to 13 carbon atoms. , an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms containing a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, and a carbon number 1 to 10 alkoxy groups, 2 to 11 carbon atoms, alkyl 1 to 10 alkyl groups, 1 to 10 carbon atoms, 2 to 11 carbon groups, carbon number 6 An aryl group of ~20, an aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and/or an electron-withdrawing group, a benzyl group substituted by an electron-donating group and/or an electron-withdrawing group, a cyano group, a methylthio group, Nitro is preferred.

Further, when R ⁶ , R ⁷ , R ⁸ and R ⁹ are groups, the two or more of them form a bond, and R ⁶ , R ⁷ , R ⁸ and R ⁹ together have atoms bonded to a benzene ring to form naphthalene, anthracene, In the case of a condensed ring such as phenanthrene or anthracene, it is also preferable from the viewpoint that the absorption wavelength becomes a long wavelength.

Preferably, R ⁶ , R ⁷ , R ⁸ and R ^{9 are} all a hydrogen atom, or any one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is a nitro group, and the other three are hydrogen atoms.

R ¹⁰ in the above formula (1) represents a hydrogen atom or an organic group.

The organic group in R ¹⁰ may, for example, be exemplified as R ¹ and R ² . The organic group may be the same as in the case of R ¹ and R ² , and may have a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

The compound represented by the above formula (1) has a -OR ¹⁰ group at the para position of the benzene ring, and therefore has good solubility in a solvent.

Among the above, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

Among the compounds represented by the above formula (1), particularly preferred For example, a compound represented by the following formula may be mentioned.

The method for synthesizing the compound represented by the above formula (1) is not particularly limited, and it can be synthesized according to the method described in the examples below.

In the photosensitive resin composition for forming an insulating film, the content of the compound represented by the above formula (1) of the component (D) is not particularly limited as long as it does not inhibit the object of the present invention. The amount of the component (D) to be used is preferably a molar ratio ((C) component content/(D) component content) of the component (C) content to the content of the component (D) of 2.5/7.5 to 9.5/0.5. It is better to be 3/7~9/1. By using the component (D) in accordance with this amount, it is easy to prepare a photosensitive resin composition having a wide exposure margin.

<(E) colorant>

The photosensitive resin composition for forming an insulating film of the present invention may further contain (E) a colorant.

The (E) coloring agent contained in the photosensitive resin composition for forming an insulating film of the present invention is not particularly limited, and for example, a colorimetric index (CI; issued by The Society of Dyers and Colourists) is used. The compounds classified by Pigment are, in particular, preferably numbered as the following colorimetric index (CI) number.

An example of a yellow pigment suitable for use is, for example, C.I. Chromatin 1 (hereinafter, CI yellow pigment, but only numbers), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71 , 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 and 185.

Examples of suitable orange pigments include, for example, C.I. Orange. Chromatin 1 (hereinafter, CI orange pigment, but only numbers), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61 , 63, 64, 71 and 73.

Examples of suitable purple pigments include, for example, C.I. Violet The coloring matter 1 (hereinafter, C.I. purple coloring, but only the number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

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

Examples of suitable blue pigments include, for example, C.I. Blue. Pigment 1 (hereinafter, C.I. blue pigment, but only numbers), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.

Examples of other hue pigments suitable for use include, for example: Green pigment such as CI green pigment 7, CI green pigment 36, CI green pigment 37, brown pigment such as CI brown pigment 23, CI brown pigment 25, CI brown pigment 26, CI brown pigment 28, CI black pigment 1, CI black pigment 7 black pigments.

Also, in the case of a coloring agent as an opacifier, a black color is used. It is preferred as an opacifier. Examples of the black pigment include metal oxides of carbon black, black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, etc., composite oxides, metal sulfides, metal sulfates or Metal carbonates and the like, regardless of various pigments of organic matter and inorganic matter. Among these, it is preferred to use carbon black having high light blocking properties.

Carbon black can be used in tank black, furnace black, hot black, lamp black, etc. Carbon black, but it is better to use groove black which is excellent in light shielding properties. Further, carbon black may be coated with a resin.

Moreover, in order to adjust the carbon black tone, the above may be appropriately added. The organic pigment acts as an auxiliary pigment.

In order to uniformly disperse the above coloring agent in the photosensitive resin group A dispersing agent can be further used in the product. As the dispersant, a polymer dispersing agent such as a polyethylenimine-based, an urethane-based or an acrylic resin is preferably used. In particular, when carbon black is used as the colorant, it is preferred to use an acrylic resin-based dispersant as a dispersant.

In addition, inorganic pigments and organic pigments may be used alone or in two The above is used together. In the case of the combined use, the organic pigment is preferably used in an amount of from 10 to 80 parts by mass, more preferably from 20 to 40 parts by mass, based on 100 parts by mass of the total of the inorganic pigment and the organic pigment.

The amount of colorant used in the photosensitive resin composition, The range of the object of the present invention is suitably selected, and the amount of use is preferably 5 to 70 parts by mass, more preferably 25 to 60 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition. .

Disperse the colorant into a suitable concentration at a suitable concentration using a dispersant After the dispersion, it is preferably added to the photosensitive resin composition.

<(F) Light Absorber>

The photosensitive resin composition for forming an insulating film of the present invention may contain (F) a light absorbing agent (hereinafter also referred to as "(F) component") as needed. (F) The light absorbing agent is not particularly limited, and those which absorb light can be used, and it is preferable to absorb light particularly in the wavelength range of 200 to 450 nm, and examples thereof include a naphthalene compound, a dinaphthyl compound, an anthraquinone compound, and a morphine. A porphyrin compound, a dye, or the like.

Specific examples thereof include α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, and 1,3-dihydroxyl group. Naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, a naphthalene derivative of 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, anthracene, 9,10-dihydroxyanthracene, or an anthracene or a derivative thereof; an azo dye, a benzophenone dye a dye such as an amine ketone dye, a quinoline dye, an anthraquinone dye, a diphenyl cyanoacrylate dye, a triazine dye, or a p-amino benzoic acid dye; Among these, a naphthalene derivative is preferred, and a hydroxy-containing naphthalene derivative is particularly preferred. These light absorbers can be used individually or in combination of 2 or more types.

The content of the component (F) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the components (A) and (B).

<(S) organic solvent>

The photosensitive resin composition for forming an insulating film of the present invention preferably contains (S) an organic solvent (hereinafter also referred to as a component (S)) for improving coating properties or viscosity.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol single Methyl 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, two Propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol single (poly)alkylene glycol monoalkyl ethers such as ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ether acetate such as acid ester, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Ester; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2- Ketones such as heptanone and 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, N-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, Other esters such as ethyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethyl Amidoxime such as formamide or N,N-dimethylacetamide; and the like. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above other ethers, alkyl lactates, and other esters mentioned above are preferred. The diol monoalkyl ether acetates, the above other ethers, and the other esters described above are more preferred. These solvents may be used alone or in combination of two or more.

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

<Other ingredients>

The photosensitive resin composition of the present invention may contain an additive such as a surfactant, an adhesion promoter, a thermal polymerization inhibitor, or an antifoaming agent. Any of the additives can be used as known in the past. The surfactant may, for example, be an anionic, cationic or nonionic compound. The adhesion promoter may, for example, be a conventionally known decane coupling agent. The thermal polymerization inhibiting agent may, for example, be hydroquinone or hydroquinone monoethyl ether. Examples of the antifoaming agent include a polyfluorene-based compound and a fluorine-based compound.

<Modulation Method of Photosensitive Resin Composition>

In the photosensitive resin composition of the present invention, the above components may be mixed (dispersed and kneaded) in a mixer such as a three-roll mill, a ball mill or a sand mill, and may be filtered and prepared by a filter such as a membrane filter of 5 μm.

≪Insulating film ≫

The insulating film of the present invention is the same as the conventional insulating film formed using the photosensitive resin composition except that the above-described photosensitive resin composition for forming an insulating film is used. Only the method of forming the insulating film will be described below.

The photosensitive resin composition for forming an insulating film described above is used. The method of forming the insulating film is not particularly limited, and can be suitably selected from conventional methods. The method of forming a suitable insulating film includes, for example, a coating step of applying a photosensitive resin composition for forming an insulating film on a substrate to form a photosensitive resin layer, and exposing the photosensitive resin layer to a pattern of a specific insulating film. The exposure step and the development step of developing the pattern of the insulating film by developing the exposed photosensitive resin layer.

First, the coating step is performed using a roll coater and reverse coating. A non-contact type coating device such as a contact transfer type coating device such as a cloth machine or a bar coater, or a rotator (rotary coating device) or a curtain coater, and the photosensitive resin composition of the present invention is applied to On the substrate on which the insulating film should be formed, the solvent may be removed by drying to form a photosensitive resin layer.

The substrate is subjected to an exposure step by forming a substrate on which a photosensitive resin layer is formed. In the exposure step, the negative-type photomask is irradiated with active energy rays such as ultraviolet rays and excimer laser light, and the photosensitive resin layer is partially exposed in accordance with the pattern of the specific insulating film. For exposure, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like can be used to emit ultraviolet light. Although the exposure amount differs depending on the composition of the photosensitive resin composition, it is preferably, for example, about 10 to 600 mJ/cm ² .

In the photosensitive resin composition described above, when the exposure portion is wide and the exposed portion is a convex portion and the unexposed portion is formed as a concave portion, the unexposed portion is hardly insolubilized to the alkali even if the exposure amount is increased. Therefore, by using the above-described photosensitive resin composition, it is easy to form a pattern in which the exposed portion is a convex portion and the unexposed portion is a concave portion. Although the unexposed portion becomes the hole pattern of the hole portion, it is particularly difficult to increase the exposure amount. Although a desired shape is formed, by using the above-described photosensitive resin composition, it is easy to form a hole pattern having a hole having a desired shape.

In the developing step, the exposed photosensitive resin layer is developed The liquid is developed to form an insulating film of a specific pattern. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developer include organic compounds such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt. Since the photosensitive resin composition of the present invention exhibits moderate developability, it can be accurately developed.

Then, if necessary, the pattern of the developed insulating film is applied After baking, it is heat-hardened. The post-baking temperature is preferably 150 to 250 ° C.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

<Examples 1 to 9 and Comparative Examples 1 to 4>

Each component shown in the following Table 1 was mixed, and the solid content was made into 24 mass %, and it melt|dissolved in the solvent, and the photosensitive resin composition was prepared. Also, PGMEA was used as a solvent.

[(A) component]

As the alkali-soluble resin of the component (A), an acrylic resin or a cardo resin described in the following Table 2 was used. The value shown in Table 2 is the content (% by mass) of each constituent unit with respect to the mass of the acrylic resin. Further, the cardo resin is a combination of the following methods.

The repeating units described in Table 2 are as follows.

(Synthesis of Cardo Resin)

First, in a 500 ml four-necked flask, 235 g of a bisphenolphthalein type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid was blown into the air at a rate of 25 ml/min, and dissolved by heating at 90 to 100 °C. Then, the solution gradually warmed up in a state of white turbidity, and was heated to 120 ° C to be completely dissolved. At this time, the solution gradually became transparent and viscous, and stirring was continued in this state. Here, the acid value is measured, and if it is less than 1.0 mgKOH/g, the heating is continued. Mixing, it takes 12 hours for the acid price to reach the target value. Thereafter, the mixture was cooled to room temperature to obtain a bisphenolphthalein type epoxy acrylate having a colorless transparent solid represented by the following formula.

Next, after dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of the above-mentioned bisphenolphthalein type epoxy acrylate, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of brominated tetra are mixed. Ethyl ammonium was gradually heated to 110-115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a cardo resin. The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

[(B) component]

The photopolymerizable monomer of the component (B) is the following.

DPHA: dipentaerythritol hexaacrylate

[(C) component]

The photopolymerization initiator of the component (C) is the following.

OXE01:1, 2-octanedione, 1-[4-(phenylsulfanyl)-, 2-(O-benzhydrylhydrazine)] ("IRGACURE OXE01" manufactured by BASF Corporation)

OXE02: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl], 1-(O-ethylindenyl) (manufactured by BASF Corporation) "IRGACURE OXE02")

NCI-831: "NCI-831" made by ADEKA

[(D) component]

In the examples and comparative examples, the compound represented by the formula (1) of the component (D) used the following MCIMA. The synthesis method of MCIMA is described below.

(Synthesis of MCIMA)

5.90 g of 3-(4-methoxyphenyl)acrylic acid chloride (30 mmol) was dissolved in 50 ml of dry ether, and 4.59 ml of triethylamine (equivalent ratio of 1.1) and 2.25 ml of imidazole (equivalent ratio of 1.1) were added. Stir at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of saturated aqueous NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate and evaporated. Purification by column chromatography using hexane-ethyl acetate as a solvent and EtOAc as a support material afforded MCIMA (3.41 g, 15 mmol).

About the photosensitivity of using Examples 1 to 9 and Comparative Examples 1 to 4 The insulating film formed of the resin composition was subjected to measurement of relative dielectric constant and evaluation of chemical resistance according to the following method. Further, the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were measured for exposure margin according to the following method.

(Method for measuring relative dielectric coefficient)

The photosensitive resin composition prepared in each of the above examples and comparative examples was spin-coated on the Shin-Etsu Chemical Industry by a rotator (MIKASA rotator IH-360S, manufactured by MIKASA Co., Ltd.) at a number of revolutions of 200 to 1000 rpm. After coating on a low-resistance substrate made by Co., Ltd., the coating film was dried at 80 ° C for 5 minutes to form a photosensitive resin layer having a film thickness of 1 μm. Next, the photosensitive resin layer was exposed by an exposure apparatus (EXM-1066, manufactured by ORC, Inc.) at an exposure amount of 50 mJ/cm ^{2 , and} the exposed photosensitive resin layer was exposed at 230 ° C for 20 minutes. After baking, an insulating film is formed. The relative dielectric constant of the formed insulating film was measured by a relative dielectric constant measuring device (SSM495, manufactured by Nippon SSM Co., Ltd.), and the measured relative dielectric constant is shown in Table 3.

(Exposure margin measurement method)

The photosensitive resin composition prepared in each of the above examples and comparative examples was spin-coated on the Shin-Etsu Chemical Industry by a rotator (MIKASA rotator IH-360S, manufactured by MIKASA Co., Ltd.) at a number of revolutions of 200 to 1000 rpm. After coating on a low-resistance substrate made by Co., Ltd., the coating film was dried at 100 ° C for 2 minutes to form a photosensitive resin layer having a film thickness of 2 to 4 μm. Then, the photosensitive resin layer was exposed by a exposure apparatus (MPA-600FA, manufactured by Canon Co., Ltd.) with a mask of 50 mJ/cm ² and a hole pattern of 5 μm in diameter. Further, in order to determine the exposure margin, the exposure amount of 50mJ / cm ² every start of 10mJ / cm ² decrease, interposed 5μm diameter hole pattern of the mask with the photosensitive resin layer is exposed. Subsequently, development was carried out by a paddle method at 23 ° C for 100 seconds by using a developing device (TR-6132U, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The developed pattern was post-baked at 230 ° C for 20 minutes to form an insulating film. The difference between the minimum exposure amount and the maximum exposure amount of the opening of the hole having a diameter of 5 μm is the exposure margin, and the measured exposure margin is shown in Table 3.

(Method for evaluating drug resistance)

The photosensitive resin composition prepared in each of the above examples and comparative examples was spin-coated on the Shin-Etsu Chemical Industry by a rotator (MIKASA rotator IH-360S, manufactured by MIKASA Co., Ltd.) at a number of revolutions of 200 to 1000 rpm. After coating on a low-resistance substrate made by Co., Ltd., the coating film was dried at 100 ° C for 2 minutes to form a photosensitive resin layer having a film thickness of 3 μm. Next, the photosensitive resin layer was exposed by an exposure apparatus (EXM-1066, manufactured by ORC, Inc.) at an exposure amount of 50 mJ/cm ^{2 , and} the exposed photosensitive resin layer was exposed at 230 ° C for 20 minutes. After baking, an insulating film is formed.

The formed insulating film was immersed in a photoresist stripping solution (ST-106, manufactured by Toho Koka Chemical Co., Ltd.) at 60 ° C for 3 minutes, and the chemical resistance was evaluated by the change in film thickness before and after the immersion. The film thickness after impregnation is less than the pre-impregnation film When the thickness was 120%, the evaluation was "○". When the film thickness after immersion was 120% or more of the film thickness before immersion, it was evaluated as "x". The results of the evaluation of chemical resistance are shown in Table 3.

According to Examples 1 to 9, it is clear that it is soluble in (A) alkali. The photosensitive resin composition of the (B) photopolymerizable monomer and (C) photopolymerization initiator is formulated (D) with a compound represented by the above formula (1), and an epoxy group is used in the resin. As the component (A), the resin having a content of 20 to 60% by mass of the constituent unit of the unsaturated compound can provide an insulating film which is excellent in chemical resistance and has a low dielectric constant and excellent insulating property, and has a wide exposure margin. A photosensitive resin composition for forming an insulating film.

According to Comparative Example 1, it is clear that the photosensitive resin composition In the case where the content of the constituent unit derived from the epoxy group-containing unsaturated compound in the resin of the component (A) is more than 60% by mass, the insulating film is formed. The relative dielectric constant becomes high and the insulation is lowered.

According to Comparative Example 2, it is clear that the photosensitive resin composition is not When (D) the compound represented by the above formula (1) is contained, the exposure margin of the photosensitive resin composition is remarkably lowered.

According to Comparative Examples 3 and 4, in the photosensitive resin group In the product, when the content of the constituent unit derived from the epoxy group-containing unsaturated compound in the resin of the component (A) is less than 20% by mass, the chemical resistance of the formed insulating film is lowered. Further, at this time, depending on the resin structure, the insulating property of the formed film is lowered or the exposure margin of the photosensitive resin composition is narrowed.

Claims (4)

A photosensitive resin composition for forming an insulating film, comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) represented by the following formula (1) The (A) alkali-soluble resin is a copolymer containing a constituent unit derived from an epoxy group-containing unsaturated compound, and the (A) alkali-soluble resin is a constituent unit derived from the epoxy group-containing unsaturated compound. The ratio is 20~60% by mass; (Wherein, R ¹ is and R ² each independently represent a hydrogen atom lines or an organic group, provided, R ¹ and R ² represents a system of at least one organic group, R ¹ and R ² may be bonded via for other to form a cyclic structure And may also contain a bond of a hetero atom; R ³ represents a single bond or an organic group; and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, and a nitrate Base, nitroso, sulfinate, sulfonate, sulfonate, phosphino, phosphinyl, phosphonium, phosphonato or organic, R ⁶ , R ⁷ , R ⁸ and R ^{The 9} series independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfonic acid group, a sulfonate group, a phosphino group, and an oxygen group. a phosphino group, a phosphonium group, a phosphonate group, an amine group, an ammonium group or an organic group. However, R ⁶ and R ^{7 are} not a hydroxyl group, and R ⁶ , R ⁷ , R ⁸ and R ⁹ may be both The bond forms a ring structure and may also contain a bond of a hetero atom; R ¹⁰ represents a hydrogen atom or an organic group). The photosensitive resin composition for forming an insulating film according to the first aspect of the invention, wherein the molar ratio of the content of the component (C) to the content of the component (D) is 2.5/7.5 to 9.5/0.5. An insulating film formed by using a photosensitive resin composition for forming an insulating film according to the first or second aspect of the patent application. A method for forming an insulating film, comprising: applying a photosensitive resin composition for forming an insulating film according to the first or second aspect of the patent application to a substrate, and forming a photosensitive resin layer; The pattern of the insulating film is an exposure step of exposing the photosensitive resin layer; and a developing step of developing a pattern of the exposed photosensitive resin layer to form an insulating film.