KR20130110103A - Photosensitive resin composition for insulating film, insulating film, and method of forming insulating film - Google Patents

Abstract

PURPOSE: A photosensitive resin composition forms an insulating film with excellent insulating properties and chemical properties and has a wide exposure margin when forming the pattern of the insulating film. CONSTITUTION: A photosensitive resin composition contains an alkali-developable resin, a photopolymerizable monomer, a photopolymerization initiator, and a compound represented by chemical formula 1. The alkali-soluble resin is a copolymer including a structure unit derived from an unsaturated compound including an epoxy group. The ratio of a structure unit derived from an unsaturated compound including the epoxy group in the alkali soluble resin is 20-60 wt%. The mole ratio of the photopolymerization initiator to the compound represented by chemical formula 1 is 2.5/7.5 - 9.5/0.5.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for forming an insulating film, a method of forming an insulating film, and a method of forming an insulating film,

The present invention relates to a photosensitive resin composition for forming an insulating film, an insulating film formed by 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.

2. Description of the Related Art Conventionally, in an electronic component such as a liquid crystal display element, an integrated circuit element, or a solid-state image pickup element, an insulating film or the like is formed between wirings in order to insulate layers arranged in layers. The insulating film is formed of various materials such as an inorganic film and an organic film, but in the case of an organic film, it is often formed using a thermosetting resin composition or a photosensitive resin composition.

The photosensitive resin composition used for forming such an insulating film is a copolymer of a monomer having an unsaturated double bond, a monomer having a carboxylic acid and an unsaturated double bond, and a monomer having a specific structure containing an allyl group, and has a molecular weight distribution (Mw / Mn) of 1.0 to 3.5, a polymerizable compound having an ethylenic unsaturated bond, and a photoinitiator (see Patent Document 1).

Japanese Patent Laid-Open Publication No. 2012-012602

However, even though the photosensitive resin composition described in Patent Document 1 can form an insulating film having good insulating property, there is a problem that the exposure margin at the time of forming the pattern of the insulating film is narrow and the degree of freedom in selecting the processing condition is low. The insulating film is required to have excellent chemical resistance because the insulating film may be exposed to various chemical solutions such as a resist stripping liquid in the processing step or the processing step of an electronic part including an insulating film. However, the photosensitive resin composition disclosed in Patent Document 1 has insufficient durability against a chemical liquid such as a resist stripping liquid.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive resin composition for forming an insulating film which can form an insulating film excellent in insulating property and chemical resistance and has a large exposure margin when forming a pattern of an insulating film. It is another object of the present invention to provide a method for forming an insulating film using the aforementioned photosensitive resin composition for forming an insulating film and a method for forming an insulating film using the above photosensitive resin composition for forming an insulating film.

The present inventors have studied hard to solve the above problems. As a result, it has been found that a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, The present inventors have found that the above problems can be solved by using a resin containing a constituent unit derived from an unsaturated compound containing an unsaturated group. Specifically, the present invention provides the following.

A first aspect of the present invention relates to a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D)

Wherein the alkali-soluble resin (A) is a copolymer comprising a constituent unit derived from an unsaturated compound containing an epoxy group,

Soluble resin is a photosensitive resin composition for forming an insulating film wherein the proportion of the constituent unit derived from the unsaturated compound containing an epoxy group in the alkali-soluble resin (A) is 20 to 60% by mass.

(Shown in, R ¹ and R ² are a hydrogen atom or an organic each independently formula: provided that at least one of R ¹ and R ² represents an organic group. R ¹ and R ² and year they are bonded form a cyclic structure may be, or may include a combination of the hetero atom. R ³ represents a single bond or an organic represents a group. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group , silanol group, represents a nitro group, a sulfinyl group, a sulfo group, sulfonate group, phosphino group, a phosphine P group, a phosphono group, phosphonate group, or an ^{organic. R 6, R 7, R} 8 And R ⁹ each independently represent a hydrogen atom, 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, a sulfo group, a sulfonate group, A phosphono group, a phosphonate group, an amino group , Ammonium represents import or an organic group. However, R ⁶ and R ⁷ is optionally, and there is no case where the hydroxyl group. R ^6, R ^7, R ⁸ and R ⁹ form a cyclic structure by the combination of these 2 or more, And R ¹⁰ represents a hydrogen atom or an organic group.

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

A third aspect of the present invention is a method for manufacturing a semiconductor device, comprising the steps of: applying a photosensitive resin composition for forming an insulating film according to the first aspect onto a substrate to form a photosensitive resin layer;

An exposure step of exposing the photosensitive resin layer according to a pattern of a predetermined insulating film,

And developing the exposed photosensitive resin layer to form a pattern of an insulating film.

According to the present invention, it is possible to provide an insulating film excellent in insulating properties and chemical resistance, and capable of providing a photosensitive resin composition for forming an insulating film having a large exposure margin when forming a pattern of an insulating film. Further, according to the present invention, it is possible to provide a method of forming an insulating film using the photosensitive resin composition for forming an insulating film and the above-described photosensitive resin composition for forming an insulating film.

&Quot; Photosensitive resin composition for forming insulating film &

(Hereinafter, also referred to as a "component (A)"), (B) a photopolymerizable monomer (hereinafter also referred to as a "photosensitive resin composition"), (Hereinafter also referred to as a "component (B)"), a photopolymerization initiator (hereinafter also referred to as "component (C)") and a compound represented by the formula (1) ). Each component contained in the photosensitive resin composition for forming an insulating film according to the present invention will be described below.

<(A) Alkali-soluble resin>

The alkali-soluble resin is a resin film having a thickness of 1 占 퐉 formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass and immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute Quot; means that the film thickness is 0.01 占 퐉 or more.

As the alkali-soluble resin (A), a copolymer containing a constituent unit derived from an unsaturated compound containing an epoxy group is used. The proportion of the constituent unit derived from an unsaturated compound containing an epoxy group in the alkali-soluble resin (A) is 20 to 60% by mass, preferably 20 to 40% by mass. By using the alkali-soluble resin (A) containing a constituent unit derived from an unsaturated compound containing an epoxy group at such a ratio, it is easy to form an insulating film having excellent insulating property by the photosensitive resin composition.

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

(a1) Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids . Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the resin to be obtained, ease of obtaining water, and the like. These (a1) unsaturated carboxylic acids may be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound (a2) include an unsaturated compound having an alicyclic epoxy group (a2-I) and an unsaturated compound having no alicyclic epoxy group (a2-II) Unsaturated compounds are preferred.

In the unsaturated compound having (a2-I) alicyclic epoxy group, the alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobonyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a2-I) alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

Specifically, examples of the unsaturated compound containing an alicyclic epoxy group (a2-I) include compounds represented by the following formulas (a2-1) to (a2-16). Among these, compounds represented by the following formulas (a2-1) to (a2-6) are preferable, and compounds represented by the following formulas (a2-1) to (a2-4) are more preferable .

Wherein 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 0 to 10 Lt; / RTI &gt; R ¹² is preferably a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene. Examples of R ¹³ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

Examples of the epoxy group-containing unsaturated compound having no (a2-II) alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (Meth) acrylic acid epoxyalkyl esters such as 7-epoxyheptyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α- And? -Alkylacrylic acid epoxyalkyl esters such as 6,7-epoxyheptyl ethyl acrylate; and the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate and 6,7-epoxyheptyl (meth) acrylate are preferred from the viewpoint of copolymerization reactivity and strength of the resin after curing Do. These epoxy group-containing unsaturated compounds having no (a2-II) alicyclic group may be used alone or in combination of two or more.

The copolymer (A1) may be obtained by polymerizing (a3) an alicyclic group-containing unsaturated compound having no epoxy group together with the unsaturated carboxylic acid (a1) and the unsaturated compound containing an epoxy group (a2).

(a3) The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include adamantyl, norbornyl, isobonyl, tricyclononyl, tricyclodecyl and tetracyclododecyl. These (a3) alicyclic group-containing unsaturated compounds may be used alone or in combination of two or more.

Specifically, (a3) the alicyclic group-containing unsaturated compound includes, for example, compounds represented by the following formulas (a3-1) to (a3-7). Among these, compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and the following formulas (a3-3) and (a3-4) are preferable from the viewpoint of easily obtaining a photosensitive resin composition having good developability. Is more preferable.

In the 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 preferably a single bond, a straight chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. As R ²³ , for example, methyl group and ethyl group are preferable.

The copolymer (A1) may be obtained by further copolymerizing a compound other than the above. Other such compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylic esters include linear or branched (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Chain alkyl (meth) acrylates such as chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (Meth) acrylate, furfuryl (meth) acrylate, and the like.

The (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (Meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

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

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- But are not limited to, ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether And vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrene include styrene, such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethyl Alkylstyrenes such as styrene, ethoxymethylstyrene and acetoxymethylstyrene, alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene and tetrachloro But are not limited to, styrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, And halostyrene such as methylstyrene.

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

The mass average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in terms of styrene conversion, in this specification) of the copolymer (A1) is preferably from 2,000 to 200,000, and more preferably from 5,000 to 30,000. Within the above range, there is a tendency that the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be balanced.

The copolymer (A1) can be produced by a known radical polymerization method. That is, they can be produced by dissolving each compound and a known radical polymerization initiator in a polymerization solvent and then heating and stirring.

The alkali-soluble resin (A) is preferably an alkali-soluble resin having a structural unit derived from the unsaturated carboxylic acid (a1), a structural unit derived from the unsaturated compound containing the epoxy group (a2) (A2) having at least a constitutional unit having a repeating unit represented by the following general formula (1) can also be suitably used. When the alkali-soluble resin (A) contains the copolymer (A2), the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing can be increased.

The copolymer (A2) is obtained by further copolymerizing (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters and styrenes described as different compounds with respect to the copolymer .

(B) a constituent unit having a polymerizable moiety with a photopolymerizable monomer is preferably an ethylenic unsaturated group as a polymerizable moiety with (B) the photopolymerizable monomer. The copolymer (A2) is obtained by reacting a part of the epoxy group in the copolymer having the constituent unit derived from the unsaturated carboxylic acid (a1) and the constituent unit derived from the unsaturated compound containing the epoxy group (a2) with the unsaturated carboxylic acid (a1) .

The mass average molecular weight of the copolymer (A2) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. Within the above range, there is a tendency that the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be balanced.

The content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 30 to 90% by mass, more preferably 45 to 75% by mass, based on the solid content of the photosensitive resin composition. In the above range, there is a tendency that the developing property tends to be balanced.

&Lt; (B) Photopolymerizable monomer &gt;

As the photopolymerizable monomer (B) contained in the photosensitive resin composition for forming an insulating film according to the present invention, a monomer having an ethylenic unsaturated group can be preferably used. Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include 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, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol 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 penta (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate (Meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide, a reaction product of 2-hydroxyethyl Polyfunctional monomers such as condensates, and triacryl amides. These multifunctional monomers may be used alone or in combination of two or more.

Among these monomers having an ethylenic unsaturated group, polyfunctional monomers having three or more functionalities are preferable, and polyfunctional monomers having six or more functional groups are preferred because of the adhesion of the photosensitive resin composition for forming an insulating film to the substrate and the strength of the photosensitive resin composition after curing. desirable.

The content of the component (B) is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, based on the solid content of the photosensitive resin composition for forming an insulating film. When the content is in the above range, there is a tendency to balance the sensitivity, developability and resolution.

<(C) Photopolymerization initiator>

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

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, 1 (9-ethyl-6-nitro-9H-carbazol-3-yl) 1- [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyloxime, Benzoyloxime)], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylamino Methylbenzoic acid, methyl benzoate, methyl benzoate, ethyl benzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, Dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- , 4-dimethylthioxanthone, 1-chloro-4-propoxycitoxone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2- 2-ethyl anthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, Benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylamino Benzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha, alpha -dichloroacetophenone, p-tert- Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4 (Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis Azine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl- 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo- - trichloromethyl-6- (2-bromo-4 -Methoxy) styrylphenyl-s-triazine. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime-type photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, particularly preferred are ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O-Acetyl oxime and 1,2-octanedione , 1- [4- (phenylthio) -, 2- (O-benzoyloxime)].

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

The photoinitiator may be combined with the component (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, Dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10- dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, Diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto-5- And thiol compounds such as methoxybenzothiazole, 3-mercaptopropionate acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate and 3-mercaptopropionate. These photoinitiators may be used alone or in combination of two or more.

&Lt; (D) Compound represented by formula (1) &gt;

The photosensitive resin composition for forming an insulating film according to 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 widened. In addition, the compound represented by the formula (1) does not adversely affect the sensitivity of the photosensitive resin composition and the obtained insulating film strength.

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

Examples of the organic group for R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

R ¹ and R ² may combine to form a cyclic structure or may further contain a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired and includes a bond including a hetero atom such as an oxygen atom, a nitrogen atom or a silicon atom . Specific examples thereof 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) R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond.

From the viewpoint of heat resistance, examples of the bond other than the hydrocarbon group in the organic group of R ¹ and R ² include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, -N═C (-R) -, -C (═NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond or a sulfinyl bond is preferable.

Substituents other than the hydrocarbon groups in the organic group of R ¹ and R ² are not particularly limited as long as the effect of the present invention is not impaired and examples thereof include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups, A silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, a carboxylate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, A sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an acyl group, an acyl group, (-NH ₂ , -NHR, -NRR ': R and R' each independently represent a hydrocarbon group), and the like can be given as examples of the alkyl group, the alkenyl group, the aryl group, . The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

Examples of substituents other than the hydrocarbon groups in the organic group of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups, cyanate groups, isocyanate groups, thiocyanate groups, A carboxyl group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, , A sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, , An arylthioether group is preferable.

Of these, at least one of R ¹ and R ² is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or may be bonded to each other to form a heterocycloalkyl group or a heteroaryl group having 2 to 20 carbon atoms Do. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group. Examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

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

Examples of the organic group for R ³ include a group for eliminating one hydrogen atom from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified as R ¹ and R ² . The organic group may be either straight chain or branched chain.

Among the above, it is preferable that R ³ is a group which removes one hydrogen atom from a single bond, an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, 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, A sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group.

Examples of the organic group for R ⁴ and R ⁵ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

Among them, 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, 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 having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, An acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR, wherein R is a hydrocarbon group), an aryl group having 6 to 20 carbon atoms, an electron donating group and / An aryl group having 6 to 20 carbon atoms which is substituted, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, a cyano group, or a methylthio group. More preferably, both of R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group, and R ⁵ is a hydrogen atom.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, Sulfo group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonia group, or organic group.

Examples of the organic group for R ⁶ , R ⁷ , R ⁸ and R ⁹ include those exemplified as R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

In the above formula (1), R ⁶ and R ⁷ do not form a hydroxyl group.

R ⁶ , R ⁷ , R ⁸ and R ⁹ may combine with each other to form a cyclic structure or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For example, R ⁶ , R ⁷ , R ^8, and R ⁹ may be bonded to each other to form an atom of a benzene ring to which R ⁶ , R ⁷ , R ^8, and R ⁹ are bonded to form an naphthalene, anthracene, phenanthrene, Or the like may be formed.

Of the above groups, 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, a cycloalkenyl group having 4 to 13 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, An alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an electron donating group and / An aryl group, an electron-donating group and / or a benzyl group substituted with an electron-withdrawing group, cyano group, methylthio group or nitro group.

In addition, R ^6, R, etc. ^7, R ⁸ and R ⁹ roneun R ^6, R ^7, R ⁸ and R ⁹ are sharing a benzene ring atom bonded naphthalene, anthracene, phenanthrene, indene combine these two or more of Even when a condensed ring is formed, the absorption wavelength is preferably long.

More preferably, all of R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is a nitro group, and the remaining three are hydrogen atoms.

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

Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

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

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

Particularly preferred specific examples among the compounds represented by the above formula (1) include compounds represented by the following formulas.

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

The content of the compound represented by the formula (1) as the component (D) in the photosensitive resin composition for forming an insulating film is not particularly limited within the range not hindering the object of the present invention. The amount of the component (D) used is preferably such that the molar ratio of the content of the component (C) to the content of the component (D) (content of the component (C) / content of the component (D)) is from 2.5 / 7.5 to 9.5 / 0.5 , And more preferably 3/7 to 9/1. By using the component (D) in such an amount, it is easy to prepare a photosensitive resin composition having a large exposure margin.

<(E) Colorant>

The photosensitive resin composition for forming an insulating film according to the present invention may further contain (E) a coloring agent.

The colorant (E) contained in the photosensitive resin composition for forming an insulating film according to the present invention is not particularly limited, and for example, a color index (CI: published by The Society of Dyers and Colourists) , Specifically those having a color index (CI) number given below are preferably used.

Examples of yellow pigments that can be used very suitably include C.I. 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, and 60 of pigment yellow 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185, have.

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

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

Examples of red pigments that can be used very suitably include C.I. Pigment Red 1 (hereinafter, &quot; CI Pigment Red &quot; is the same and only the numbers are described below), 2,3,4,5,6,7,8,9,10,11,12,14,15,16, 48, 48: 3,4: 48,4: 49: 1, 49: 1, 48: 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of blue pigments which can be used very suitably include C.I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only the numbers are listed), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, have.

Examples of pigments of other colors which can be used very suitably include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

When a colorant is used as the light shielding agent, it is preferable to use a black pigment as the light shielding agent. Examples of the black pigment include organic pigments such as carbon black, perylene black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates, , And various pigments regardless of the inorganic matter. 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 channel black excellent in light shielding property. Resin-coated carbon black may also be used.

In order to adjust the color tone of the carbon black, the above organic pigment may be suitably added as an auxiliary pigment.

In order to uniformly disperse the above coloring agent in the photosensitive resin composition, a dispersing agent may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of a polyethylene imine type, a urethane resin type or an acrylic resin type. Particularly, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, the organic pigments are preferably used in an amount of from 10 to 80 parts by mass per 100 parts by mass of the total amount of the inorganic pigments and the organic pigments, And more preferably in the range of 20 to 40 parts by mass.

The amount of the coloring agent to be used in the photosensitive resin composition may be appropriately selected so as not to impair the object of the present invention. Typically, it is preferably 5 to 70 parts by mass relative to 100 parts by mass of the total amount of the solid components of the photosensitive resin composition, To 60 parts by mass is more preferable.

The colorant is preferably added to the photosensitive resin composition after preparing a dispersion in which the colorant is dispersed at a suitable concentration using a dispersant.

&Lt; (F) Light absorber &gt;

The photosensitive resin composition for forming an insulating film according to the present invention may contain (F) a light absorbent (hereinafter also referred to as &quot; component (F) &quot; (F) The light absorbing agent is not particularly limited, and any material capable of absorbing exposure light can be used. In particular, it is preferable to absorb light in a wavelength range of 200 to 450 nm. Examples thereof include naphthalene compounds, dinaphthalene compounds, anthracene compounds, phenanthroline compounds, and dyes.

Specific examples include α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, Naphthalene derivatives such as hydroxynaphthalene, 2,7-dihydroxynaphthalene, anthracene and 9,10-dihydroxyanthracene, anthracene or derivatives thereof, azo dyes, benzophenone dyes, amino ketone dyes, quinoline dyes , Dyes such as anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes and p-aminobenzoic acid dyes. Among them, it is preferable to use a naphthalene derivative, and a naphthalene derivative having a hydroxyl group is particularly preferable. These light absorbers may be used alone or in combination of two or more.

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

<(S) Organic solvents>

The photosensitive resin composition for forming an insulating film according to the present invention preferably contains (S) an organic solvent (hereinafter also referred to as an "(S) component") for improving the applicability and adjusting the 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, 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- propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, Glycol monomethyl ether, tripropylene glycol monoethyl ether and the like Alkylene glycol monoalkyl ethers 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 (PGMEA) (Poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, and other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate, ethyl 2-hydroxy- , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl- Propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-propyl acetate, n- Other esters such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate ; Aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. Of these, alkylene glycol monoalkyl ether acetates, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, alkyl ester of lactic acid and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, One other ether, and the other esters described above are more preferable. These solvents may be used alone or in combination of two or more.

The content of the component (S) is not particularly limited and is appropriately set in accordance with the coating film thickness at a concentration applicable to a substrate or the like. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and even more preferably 20 to 30 cp. The solid concentration is preferably 5 to 100% by mass, and more preferably 20 to 50% by mass.

&Lt; Other components &gt;

The photosensitive resin composition according to the present invention may contain an additive such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and a defoaming agent, if necessary. Any additive may be any conventionally known one. Examples of the surfactant include anionic, cationic, and nonionic surfactants. Examples of the adhesion improver include conventionally known silane coupling agents. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, and the like. Examples of the antifoaming agent include silicon compounds and fluorine compounds.

&Lt; Preparation method of photosensitive resin composition &gt;

The photosensitive resin composition according to the present invention can be prepared by mixing (dispersing and kneading) each of the above components with a stirrer such as a three-roll mill, a ball mill or a sand mill, filtering the mixture with a filter such as a 5 μm membrane filter have.

«Insulating film»

The insulating film according to the present invention is the same as the conventional insulating film formed by using the photosensitive resin composition except that the above-described photosensitive resin composition for forming an insulating film is used. Hereinafter, only a method of forming an insulating film will be described.

The method for forming the insulating film using the above-described photosensitive resin composition for forming an insulating film is not particularly limited and may be suitably selected from conventional methods. A preferable method of forming the insulating film includes a coating step of applying the above-described photosensitive resin composition for forming an insulating film onto a substrate to form a photosensitive resin layer, an exposure step of exposing the photosensitive resin layer according to a pattern of a predetermined insulating film, And a developing step of developing the photosensitive resin layer to form a pattern of the insulating film.

First, in the coating step, a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), or a curtain flow coater is used on a substrate on which an insulating film is to be formed And the solvent is removed by drying as required to form a photosensitive resin layer.

Next, a substrate provided with a photosensitive resin layer on its surface is provided in an exposure process. In the exposure step, an active energy ray such as ultraviolet rays or excimer laser light is irradiated to the photosensitive resin layer through a negative type mask to partially expose the photosensitive resin layer according to a pattern of a predetermined insulating film. For exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, or the like can be used. The exposure dose varies depending on the composition of the photosensitive resin composition but is preferably, for example, about 10 to 600 mJ / cm 2.

Since the photosensitive resin composition described above has a wide exposure margin, it is difficult for the unexposed portion to be insolubilized with respect to alkali even when the exposure portion is formed as a convex portion and the pattern having the concave portion as the unexposed portion is formed. Therefore, by using the above-described photosensitive resin composition, it is easy to form a pattern having the exposed portion as the convex portion and the unexposed portion as the concave portion as a good-shaped pattern. In the hole pattern having the unexposed portion as a hole portion, it is difficult to form a hole having a desired shape particularly when the exposure amount is increased. However, it is easy to form a hole pattern having a hole having a desired shape by using the photosensitive resin composition described above.

In the developing step, the exposed photosensitive resin layer is developed with a developing solution to form an insulating film of a predetermined pattern. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. The photosensitive resin composition according to the present invention exhibits appropriate developability, so that appropriate development is possible.

If necessary, post-baking is performed on the pattern of the insulating film after the development, followed by heating and curing. The temperature of the post-baking is preferably 150 to 250 ° C.

Example

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

< Example  1 to 9, Comparative Example  1 to 4>

Each component shown in Table 1 below was mixed and dissolved in a solvent such that the solid content was 24% by mass to prepare a photosensitive resin composition. In addition, PGMEA was used as a solvent.

[Component (A)] [

As the alkali-soluble resin as the component (A), the acrylic resin or the carboxyl resin described in the following Table 2 was used. The values shown in Table 2 are the content (mass%) of each constituent unit with respect to the mass of the acrylic resin. The cardo resin was synthesized by the following method.

The repeating units shown in Table 2 are as follows.

(Synthesis method of cardo resin)

235 g of bisphenol fluorene 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 were placed in a 500 ml four- With stirring at a rate of 25 ml / min. Then, the solution was slowly heated to a cloudy state and heated to 120 캜 to be completely dissolved. At this time, the solution gradually became a transparent point group, but stirring was continued. During this time, the acid value was measured and the heating and stirring were continued until it was less than 1.0 mg KOH / g. It took 12 hours to reach the target price. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula which was colorless transparent and solid.

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. Then, The reaction was allowed to proceed at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a cardboard resin. The disappearance of the acid anhydride group was confirmed by IR spectrum.

[Component (B)] [

The following photopolymerizable monomer (B) was used.

DPHA: dipentaerythritol hexaacrylate

[Component (C)] [

The following photopolymerization initiator was used as the component (C).

OXE01: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (IRGACURE OXE01,

(OXE02: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

NCI-831: "NCI-831" manufactured by ADEKA

[Component (D)] [

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

(Synthesis method of MCIMA)

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml (equivalent ratio 1.1) Lt; / RTI &gt; 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain MCIMA (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

The dielectric constant of the insulating film formed using the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 was measured according to the following method and the chemical resistance was evaluated. In addition, for the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4, the exposure margin was measured by the following method.

(Relative dielectric constant measurement method)

The photosensitive resin compositions prepared in the above Examples and Comparative Examples were spin-coated on a low-resistance substrate of Shin-Etsu Chemical Co., Ltd. with a spinner (Micasa Spinner IH-360S, manufactured by Mikasa) at a rotation speed of about 200 to 1000 rpm Then, the coated film was dried at 80 DEG C for 5 minutes to form a photosensitive resin layer having a thickness of 1 mu m. Next, the photosensitive resin layer was exposed to light at an exposure dose of 50 mJ / cm 2 by an exposure apparatus (EXM-1066, manufactured by Oak Production Co., Ltd.). Post-baking was performed on the exposed photosensitive resin layer at 230 캜 for 20 minutes to form an insulating film. The relative dielectric constant of the formed insulating film was measured by a specific permittivity measuring device (SSM495, manufactured by SSM Corporation, Japan). The measured relative permittivities are listed in Table 3.

(Exposure margin measurement method)

The photosensitive resin compositions prepared in the above Examples and Comparative Examples were spin-coated on a substrate made by Shin-Etsu Chemical Co., Ltd. at a rotation speed of about 200 to 1000 rpm using a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Co., Ltd.) And dried at 100 DEG C for 2 minutes to form a photosensitive resin layer having a thickness of 2 to 4 mu m. Next, the photosensitive resin layer was exposed to light through a hole pattern mask having a diameter of 5 mu m at an exposure amount of 50 mJ / cm2 by an exposure apparatus (MPA-600FA, manufactured by Canon Inc.). In order to determine the exposure margin, the photosensitive resin layer was exposed through a hole pattern mask having a diameter of 5 탆 by increasing and decreasing the exposure amount from 50 mJ / cm 2 to 10 mJ / cm 2. Next, development was carried out by a paddle method at 23 DEG C for 100 seconds using a developing device (TR-6132U, manufactured by Tokyo Oka Kogyo Co., Ltd.). Post-baking was performed on the developed pattern under the condition of 230 占 폚 for 20 minutes to form an insulating film. The difference between the minimum exposure dose and the maximum exposure dose at which holes with a diameter of 5 占 퐉 could be opened was defined as an exposure margin. Table 3 shows the measured exposure margins.

(Chemical resistance evaluation method)

The photosensitive resin compositions prepared in the above Examples and Comparative Examples were spin-coated on a substrate made by Shin-Etsu Chemical Co., Ltd. at a rotation speed of about 200 to 1000 rpm by using a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Co., Ltd.) And dried at 100 캜 for 2 minutes to form a photosensitive resin layer having a thickness of 3 탆. Next, the photosensitive resin layer was exposed to light at an exposure dose of 50 mJ / cm 2 by an exposure apparatus (EXM-1066, manufactured by Oak Production Co., Ltd.). Post-baking was performed on the exposed photosensitive resin layer at 230 캜 for 20 minutes to form an insulating film.

The resulting insulating film was immersed in a resist stripping solution (ST-106, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 60 캜 for 3 minutes, and the chemical resistance was evaluated by a change in film thickness before and after immersion. A case where the film thickness after immersion was less than 120% of the film thickness before immersion was evaluated as &quot;? &Quot;. The case where the film thickness after immersion was 120% or more of the film thickness before immersion was evaluated as &quot; x &quot;. The evaluation results of the chemical resistance are shown in Table 3.

According to Examples 1 to 9, a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, (D) a compound represented by the aforementioned formula (1) By using a resin having 20 to 60 mass% of a constituent unit derived from an unsaturated compound containing an epoxy group in the resin as the component (A), an insulating film excellent in chemical resistance, low in dielectric constant and excellent in insulation can be formed And a photosensitive resin composition for forming an insulating film having a wide exposure margin can be obtained.

According to Comparative Example 1, when the content of the constituent unit derived from the unsaturated compound containing an epoxy group in the resin as the component (A) in the photosensitive resin composition exceeds 60% by mass, the relative dielectric constant of the insulating film to be formed becomes high, .

According to Comparative Example 2, when the photosensitive resin composition does not contain the compound represented by the above-mentioned formula (1) (D), the exposure margin of the photosensitive resin composition remarkably decreases.

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

Claims (4)

(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D)
Wherein the alkali-soluble resin (A) is a copolymer comprising a constituent unit derived from an unsaturated compound containing an epoxy group,
Wherein the ratio of the constituent unit derived from the unsaturated compound containing an epoxy group in the alkali-soluble resin (A) is 20 to 60% by mass.

(Shown in, R ¹ and R ² are a hydrogen atom or an organic each independently formula: provided that at least one of R ¹ and R ² represents an organic group. R ¹ and R ² and year they are bonded form a cyclic structure may be, or may include a combination of the hetero atom. R ³ represents a single bond or an organic represents a group. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group , silanol group, represents a nitro group, a sulfinyl group, a sulfo group, sulfonate group, phosphino group, a phosphine P group, a phosphono group, phosphonate group, or an ^{organic. R 6, R 7, R} 8 And R ⁹ each independently represent a hydrogen atom, 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, a sulfo group, a sulfonate group, A phosphono group, a phosphonate group, an amino group , Ammonium represents import or an organic group. However, R ⁶ and R ⁷ is optionally, and there is no case where the hydroxyl group. R ^6, R ^7, R ⁸ and R ⁹ form a cyclic structure by the combination of these 2 or more, And R ¹⁰ represents a hydrogen atom or an organic group. The method according to claim 1,
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 using the photosensitive resin composition for forming an insulating film according to claim 1 or 2. A coating step of applying the photosensitive resin composition for forming an insulating film according to claim 1 or 2 on a substrate to form a photosensitive resin layer;
An exposure step of exposing the photosensitive resin layer according to a pattern of a predetermined insulating film,
And developing the exposed photosensitive resin layer to form a pattern of an insulating film.